Methods and materials for fabricating laminate nanomolds and nanoparticles therefrom

ABSTRACT

A laminate nanomold includes a layer of perfluoropolyether defining a cavity that has a predetermined shape and a support layer coupled with the layer of perfluoropolyether. The laminate can also include a tie-layer coupling the layer of perfluoropolyether with the support layer. The tie-layer can also include a photocurable component and a thermal curable component. The cavity can have a broadest dimension of less than 500 nanometers.

TECHNICAL FIELD

Generally, the present invention relates to materials and methods forfabricating molds having nano-sized cavities for molding nanoparticlestherein. More particularly, the molds include laminated layers ofpolymeric materials and can include arrays of nano-sized cavities ofpredetermined shapes.

ABBREVIATIONS

-   -   AC=alternating current    -   Ar=Argon    -   ° C.=degrees Celsius    -   cm=centimeter    -   8-CNVE=perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene)    -   CSM=cure site monomer    -   CTFE=chlorotrifluoroethylene    -   g=grams    -   h=hours    -   1-HPFP=1,2,3,3,3-pentafluoropropene    -   2-HPFP=1,1,3,3,3-pentafluoropropene    -   HFP=hexafluoropropylene    -   HMDS=hexamethyldisilazane    -   IL=imprint lithography    -   IPDI=isophorone diisocyanate    -   MCP=microcontact printing    -   Me=methyl    -   MEA=membrane electrode assembly    -   MEMS=micro-electro-mechanical system    -   MeOH=methanol    -   MIMIC=micro-molding in capillaries    -   mL=milliliters    -   mm=millimeters    -   mmol=millimoles    -   M_(n)=number-average molar mass    -   m.p.=melting point    -   mW=milliwatts    -   NCM=nano-contact molding    -   NIL=nanoimprint lithography    -   nm=nanometers    -   Pd=palladium    -   PAVE perfluoro(alkyl vinyl)ether    -   PDMS=poly(dimethylsiloxane)    -   PEM=proton exchange membrane    -   PFPE=perfluoropolyether    -   PMVE perfluoro(methyl vinyl)ether    -   PPVE perfluoro(propyl vinyl)ether    -   PSEPVE=perfluoro-2-(2-fluorosulfonylethoxy)propyl vinyl ether    -   PTFE=polytetrafluoroethylene    -   SAMIM=solvent-assisted micro-molding    -   SEM=scanning electron microscopy    -   Si=silicon    -   TFE=tetrafluoroethylene    -   μm=micrometers    -   UV=ultraviolet    -   W=watts

BACKGROUND

Polymer materials have been used as molds and as laminate molds for manyyears. However, the typical polymer molds and laminate molds have manydrawbacks with respect to the scale of what can be molded therein. Suchdrawbacks generally result from chemical and physical interactionbetween the materials of the molds and the materials being moldedtherein. Typically, as the structures to be molded are reduced in sizeand approach tens or hundreds of micrometers or less, the typical moldmaterials fail to perform as molds. These failures can include thefailure to accept material into such mold cavities and failure torelease, especially release cleanly, any materials that do enter themold cavities. Therefore, there is a need in the art for materials thatcan form molds having cross-sectional dimensions of less than tens ofmicrometers, less than micrometers, and less than 500 nanometers thatcan accept materials into mold cavities and cleanly release materialsmolded therein. Furthermore, the smaller the feature sizes of thearticle being formed in the mold, the closer that feature size comes todefects and blemishes produced by the conventional molding materials andmethods.

The applicants have previously disclosed PFPE based materials thatovercome these drawbacks and disclose herein further methods, materials,and articles for overcoming such drawbacks.

SUMMARY

According to the present invention, a laminate nanomold includes a layerof perfluoropolyether, where the layer of perfluoropolyether defines acavity having a predetermined shape and a support layer coupled with thelayer of perfluoropolyether. In some embodiments, the laminate alsoincludes a tie-layer coupling the layer of perfluoropolyether with thesupport layer. According to other embodiments, the tie-layer includes aphotocurable component and a thermal curable component.

In some embodiments, the laminate further includes a plurality ofcavities defined in the perfluoropolyether layer. Each cavity of theplurality of cavities can have a predetermined shape selected from thegroup of cylindrical, 200 nm diameter cylinders, cuboidal, 200 nmcuboidal, crescent, and concave disc. In some embodiments, the pluralityof cavities includes cavities of a variety of predetermined shapes.According to alternative embodiments, each cavity of the plurality ofcavities is less than about 10 micrometers in a largest dimension, lessthan about 5 micrometers in a largest dimension, less than about 1micrometer in a largest dimension, less than about 750 nanometers in alargest dimension, less than about 500 nanometers in a largestdimension, less than about 300 nanometers in a largest dimension, lessthan about 200 nanometers in a largest dimension, less than about 100nanometers in a largest dimension, less than about 75 nanometers in alargest dimension, less than about 50 nanometers in a largest dimension,less than about 40 nanometers in a largest dimension, less than about 30nanometers in a largest dimension, less than about 20 nanometers in alargest dimension, or less than about 10 nanometers in a largestdimension.

According to other embodiments, the perfluoropolyether layer is lessthan about 50 micrometers thick, less than about 40 micrometers thick,less than about 30 micrometers thick, less than about 20 micrometersthick, less than about 15 micrometers thick, less than about 10micrometers thick.

In some embodiments, the support layer includes a polymer. In otherembodiments, the polymer of the support layer includes polyethyleneterephthalate. In alternative embodiments, the support layer is lessthan about 20 mil thick, less than about 15 mil thick, less than about10 mil thick, or less than about 5 mil thick.

In certain embodiments, the support layer introduces a modulus ofgreater than 1000 to the laminate. In other embodiments, the layer ofperfluoropolyether is coupled with the support layer by photoinitiatorcoupling and thermalinitiator coupling. In some embodiments, theperfluoropolyether includes a photocurable component. In yet otherembodiments, the layer of perfluoropolyether has a footprint greaterthan about 25 square centimeters, a footprint greater than about 50square centimeters, or a footprint greater than about 100 squarecentimeters.

In some embodiments, each cavity of the plurality of cavities is lessthan about 5 micrometers from an adjacent cavity, less than about 2micrometer from an adjacent cavity, less than about 1 micrometers froman adjacent cavity, less than about 750 nanometers from an adjacentcavity, or less than about 500 nanometers from an adjacent cavity. Insome embodiments, the perfluoropolyether has less than about 10 percentsol fraction.

According to other embodiments of the present invention, a method ofmaking a laminate nanomold includes positioning a patterned masteradjacent to a support layer, inserting the positioned patterned masterand adjacent support layer between nips of a roll laminator, deliveringa curable perfluoropolyether between the patterned master and thesupport layer adjacent an input side of the roll laminator, activatingthe roll laminator to laminate the patterned master with the supportlayer, wherein the curable perfluoropolyether is dispersed between thepatterned master and the support layer, and treating the laminate toactivate a curable component of the curable perfluoropolyether such thatthe perfluoropolyether is solidified. In some embodiments, the methodfurther includes, before positioning the patterned master adjacent thesupport layer, configuring a tie-layer with the support layer such thatwhen activated the curable perfluoropolyether binds with the tie-layer.

According to further embodiments of the present invention, a laminatepolymer mold includes a first polymer layer coupled to a second polymerlayer by a tie-layer disposed between the first polymer layer and thesecond polymer layer, wherein the tie-layer includes a fluoropolymerhaving a photocurable component and a thermal curable component. In someembodiments, the polymer of the first or second layers includes afluoropolymer. In other embodiments, the polymer of the first or secondlayers includes a perfluoropolyether. In further embodiments, thepolymer of the first or second layers includes a polyethyleneterephthalate. In still further embodiments, the fluoropolymer of thetie-layer includes a perfluoropolyether.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic of a laminate mold according to an embodimentof the present invention;

FIG. 2 is a schematic of a roll apparatus for fabricating a laminatemold according to an embodiment of the present invention;

FIG. 3 is a schematic of a roll apparatus for fabricating a laminatemold according to another embodiment of the present invention;

FIG. 4 is a schematic of separation of a laminate mold from a mastertemplate according to an embodiment of the present invention;

FIG. 5 is an SEM image of a top surface of a laminate mold having 200 nmcavities arranged in a hexagonal array according to an embodiment of thepresent invention;

FIG. 6 is an SEM image of a polymer replica fabricated from the laminatemold of FIG. 5 showing hexagonally arranged 200 nm posts formed from the200 nm cavities of the laminate mold; and

FIGS. 7A and 7B are graphs showing sample IR data according to anembodiment of the present invention.

DETAILED DESCRIPTION

Generally, the present invention discloses laminate molds of varyingpolymer materials and methods of making such molds. The molds generallyinclude arrays of nano-sized cavities formed with predetermined shapesand controlled spacing between the cavities.

I. Non-Exhaustive List of Definitions

As used herein, the term “pattern” can mean an array, a matrix, specificshape or form, a template of the article of interest, or the like. Insome embodiments, a pattern can be ordered, uniform, repetitious,alternating, regular, irregular, or random arrays or templates. Thepatterns of the present invention can include one or more of a micro- ornano-sized reservoir, a micro- or nano-sized reaction chamber, a micro-or nano-sized mixing chamber, a micro- or nano-sized collection chamber.The patterns of the present invention can also include a surface textureor a pattern on a surface that can include micro- and/or nano-sizedcavities. The patterns can also include micro- or nano-sizedprojections.

As typical in polymer chemistry the term “perfluoropolyethers” hereinshould be understood to represent not only its purest form, i.e., thepolymeric chain built from three elements—carbon, oxygen, and fluorine,but variations of such structures. The base family ofperfluooropolyethers itself includes linear, branched, andfunctionalized materials. The use within this patent also includes somesubstitution of the fluorine with materials such as H, and otherhalides; as well as block or random copolymers to modify the baseperfluoropolyethers.

As used herein, the term “monolithic” refers to a structure having oracting as a single, uniform structure.

As used herein, the term “non-biological organic materials” refers toorganic materials, i.e., those compounds that include covalentcarbon-carbon bonds, other than biological materials. As used herein,the term “biological materials” includes nucleic acid polymers (e.g.,DNA, RNA) amino acid polymers (e.g., enzymes, proteins, and the like)and small organic compounds (e.g., steroids, hormones) wherein the smallorganic compounds have biological activity, especially biologicalactivity for humans or commercially significant animals, such as petsand livestock, and where the small organic compounds are used primarilyfor therapeutic or diagnostic purposes. While biological materials areof interest with respect to pharmaceutical and biotechnologicalapplications, a large number of applications involve chemical processesthat are enhanced by other than biological materials, i.e.,non-biological organic materials.

As used herein, the term “partial cure” refers to a condition whereinless than about 100% of a polymerizable group of a material is reacted.In certain embodiments, the term “partially-cured material” refers to amaterial that has undergone a partial cure process or treatment.

As used herein, the term “full cure” refers to a condition wherein about100% of a polymerizable group of a material is reacted. In certainembodiments, the term “fully-cured material” refers to a material whichhas undergone a full cure process or treatment.

As used herein, the term “photocured” refers to a reaction ofpolymerizable groups whereby the reaction can be triggered by actinicradiation, such as UV light. In this application UV-cured can be asynonym for photocured.

As used herein, the term “thermal cure” or “thermally cured” refers to areaction of polymerizable groups, whereby the reaction can be triggeredor accelerated by heating the material beyond a threshold temperature.

Following long-standing patent law convention, the terms “a”, “an”, and“the” refer to “one or more” when used in this application, includingthe claims. Thus, for example, reference to “a cavity” includes aplurality of such cavities, and so forth.

II. Materials

In certain embodiments, the present invention broadly describes andemploys solvent resistant, low surface energy polymeric materials forfabricating articles or articles, such as molds having micro- and/ornano-sized cavities. According to some embodiments the low surfaceenergy polymeric materials include, but are not limited tofluoropolyether or perfluoropolyether (collectively “PFPE”),poly(dimethylsiloxane) (PDMS), poly(tetramethylene oxide), poly(ethyleneoxide), poly(oxetanes), polyisoprene, polybutadiene, fluoroolefin-basedfluoroelastomers, and the like. An example of forming a mold with suchmaterials includes casting liquid PFPE precursor materials onto apatterned substrate (or master) and then curing the liquid PFPEprecursor materials to generate a replica pattern of the master. Forsimplification purposes, most of the description will focus on PFPEmaterials, however, it should be appreciated that other polymers, suchas those recited herein, can be applied to the methods, materials, andarticles of the present invention.

According to certain embodiments of the present invention, “curing” aliquid polymer, for example a liquid PFPE precursor, means transformingthe polymer from a liquid state to a non-liquid state (excluding a gasstate) such that the polymer does not readily flow, such as a materialwith a relatively high viscosity or a rubbery state. In someembodiments, the non-liquid state that the polymer is transformed to isa gel state. In some embodiments, the polymer in the non-liquid statecan include un-reacted polymerizable groups. In other embodiments, thepolymer liquid precursor is capable of undergoing a first cure to becomenon-liquid such that the polymer becomes not fully soluble in a solvent.In other embodiments, when the liquid polymer precursor is cured it ismeant that the polymer has transitioned into a non-liquid polymer thatforms fibers about an object drawn through the material. In otherembodiments, an initial cure of the liquid polymer precursor transitionsthe polymer to a non-conformable state at room temperature. In otherembodiments, following a cure, the polymer takes a gel form, wherein gelmeans an article that is free-standing or self-supporting in that itsyield value is greater than the shear stress imposed by gravity.

Representative solvent resistant elastomer-based materials include butare not limited to fluorinated elastomer-based materials. As usedherein, the term “solvent resistant” refers to a material, such as anelastomeric material that does not substantially swell or dissolve incommon hydrocarbon-based organic solvents or acidic or basic aqueoussolutions. Representative fluorinated elastomer-based materials includebut are not limited to fluoropolyether and perfluoropolyether(collectively “PFPE”) based materials.

In certain embodiments, functional liquid PFPE materials exhibitdesirable properties for use in a micro- or nano-sized molds. Forexample, functional PFPE materials typically have one or more of thefollowing characteristics: low surface energy, are non-toxic, UV andvisible light transparent, highly gas permeable, cure into a tough,durable, highly fluorinated elastomeric or glassy materials withexcellent release properties, resistant to swelling, solvent resistant,biocompatible, non-reactive surfaces, combinations thereof, and thelike. The properties of these materials can be tuned over a wide rangethrough the judicious choice of additives, fillers, reactiveco-monomers, and functionalization agents, examples of which aredescribed further herein. Such properties that are desirable to modify,include, but are not limited to, modulus, tear strength, surface energy,permeability, functionality, mode of cure, solubility, toughness,hardness, elasticity, swelling characteristics, absorption, adsorption,combinations thereof, and the like.

Some examples of methods of adjusting mechanical and or chemicalproperties of the finished material includes, but are not limited to,shortening the molecular weight between cross-links to increase themodulus of the material, adding monomers that form polymers of high Tgto increase the modulus of the material, adding charged monomer orspecies to the material to increase the surface energy or wetability ofthe material, combinations thereof, and the like.

According to one embodiment, materials for use herein (e.g., PFPEmaterials) have surface energy below about 30 mN/m. According to anotherembodiment the surface energy is between about 7 mN/m and about 20 mN/m.According to a more preferred embodiment, the surface energy is betweenabout 10 mN/m and about 15 mN/m. The non-swelling nature and easyrelease properties of the presently disclosed materials (e.g. PFPEmaterials) allow for the fabrication of laminate articles.

II.A. Perfluoropolyether Materials Prepared from a Liquid PFPE PrecursorMaterial Having a Viscosity Less Than About 100 Centistokes.

As would be recognized by one of ordinary skill in the art,perfluoropolyethers (PFPEs) have been in use for over 25 years for manyapplications. Commercial PFPE materials are made by polymerization ofperfluorinated monomers. The first member of this class was made by thecesium fluoride catalyzed polymerization of hexafluoropropene oxide(HFPO) yielding a series of branched polymers designated as KRYTOX®(DuPont, Wilmington, Del., United States of America). A similar polymeris produced by the UV catalyzed photo-oxidation of hexafluoropropene(FOMBLIN® Y) (Solvay Solexis, Brussels, Belgium). Further, a linearpolymer (FOMBLIN® Z) (Solvay) is prepared by a similar process, bututilizing tetrafluoroethylene. Finally, a fourth polymer (DEMNUM®)(Daikin Industries, Ltd., Osaka, Japan) is produced by polymerization oftetrafluorooxetane followed by direct fluorination. Structures for thesefluids are presented in Table I. Table II contains property data forsome members of the PFPE class of lubricants. Likewise, the physicalproperties of functional PFPEs are provided in Table III. In addition tothese commercially available PFPE fluids, a new series of structures arebeing prepared by direct fluorination technology. Representativestructures of these new PFPE materials appear in Table IV. Of theabovementioned PFPE fluids, only KRYTOX® and FOMBLIN® Z have beenextensively used in applications. See Jones, W. R., Jr., The Propertiesof Perfluoropolyethers Used for Space Applications, NASA TechnicalMemorandum 106275 (July 1993), which is incorporated herein by referencein its entirety. Accordingly, the use of such PFPE materials is providedin the presently disclosed subject matter.

TABLE I NAMES AND CHEMICAL STRUCTURES OF COMMERCIAL PFPE FLUIDS NAMEStructure DEMNUM ® C₃F₇O(CF₂CF₂CF₂O)_(x)C₂F₅ KRYTOX ®C₃F₇O[CF(CF₃)CF₂O]_(x)C₂F₅ FOMBLIN ® YC₃F₇O[CF(CF₃)CF₂O]_(x)(CF₂O)_(y)C₂F₅ FOMBLIN ® ZCF₃O(CF₂CF₂O)_(x)(CF₂O)_(y)CF₃

TABLE II PFPE PHYSICAL PROPERTIES Average Viscosity Pour Vapor Pressure,Molecular at 20° C., Viscosity Point, Torr Lubricant Weight (cSt) Index° C. 20° C. 100° C. FOMBLIN ® 9500 255 355 −66 2.9 × 10⁻¹² 1 × 10⁻⁸ Z-25KRYTOX ® 3700 230 113 −40 1.5 × 10⁻⁶ 3 × 10⁻⁴ 143AB KRYTOX ® 6250 800134 −35   2 × 10⁻⁸ 8 × 10⁻⁶ 143AC DEMNUM ® 8400 500 210 −53   1 × 10⁻¹⁰1 × 10⁻⁷ S-200

TABLE III PFPE PHYSICAL PROPERTIES OF FUNCTIONAL PFPEs Average ViscosityMolecular at 20° C., Vapor Pressure, Torr Lubricant Weight (cSt) 20° C.100° C. FOMBLIN ® 2000 85 2.0 × 10⁻⁵ 2.0 × 10⁻⁵ Z-DOL 2000 FOMBLIN ®2500 76 1.0 × 10⁻⁷ 1.0 × 10⁻⁴ Z-DOL 2500 FOMBLIN ® 4000 100 1.0 × 10⁻⁸1.0 × 10⁻⁴ Z-DOL 4000 FOMBLIN ® 500 2000 5.0 × 10⁻⁷ 2.0 × 10⁻⁴ Z-TETROL

TABLE IV Names and Chemical Structures of Representative PFPE FluidsName Structure^(a) Perfluoropoly(methylene oxide) (PMO)CF₃O(CF₂O)_(x)CF₃ Perfluoropoly(ethylene oxide) (PEO)CF₃O(CF₂CF₂O)_(x)CF₃ Perfluoropoly(dioxolane) (DIOX)CF₃O(CF₂CF₂OCF₂O)_(x)CF₃ Perfluoropoly(trioxocane) (TRIOX)CF₃O[(CF₂CF₂O)₂CF₂O]_(x)CF₃ ^(a)wherein x is any integer.

In some embodiments, the perfluoropolyether precursor includespoly(tetrafluoroethylene oxide-co-difluoromethylene oxide)α,ω diol,which in some embodiments can be photocured to form one of aperfluoropolyether dimethacrylate and a perfluoropolyether distyreniccompound. A representative scheme for the synthesis and photocuring of afunctionalized perfluoropolyether is provided in Scheme 1.

II.B. Perfluoropolyether Materials Prepared from a Liquid PFPE PrecursorMaterial Having a Viscosity Greater Than About 100 Centistokes.

The methods provided herein below for promoting and/or increasingadhesion between a layer of a PFPE material and another material and/ora substrate and for adding a chemical functionality to a surface includea PFPE material having a characteristic selected from the groupincluding, but not limited to a viscosity greater than about 100centistokes (cSt) and a viscosity less than about 100 cSt, provided thatthe liquid PFPE precursor material having a viscosity less than 100 cStis not a free-radically photocurable PFPE material. As provided herein,the viscosity of a liquid PFPE precursor material refers to theviscosity of that material prior to functionalization, e.g.,functionalization with a methacrylate or a styrenic group.

Thus, in some embodiments, PFPE material is prepared from a liquid PFPEprecursor material having a viscosity greater than about 100 centistokes(cSt). In some embodiments, the liquid PFPE precursor is end-capped witha polymerizable group. In some embodiments, the polymerizable group isselected from the group including, but not limited to an acrylate, amethacrylate, an epoxy, an amino, a carboxylic, an anhydride, amaleimide, an isocyanato, an olefinic, and a styrenic group. In someembodiments, the PFPE material includes a backbone structure selectedfrom the group including, but not limited to:

wherein X is present or absent, and when present includes an endcappinggroup, and n is an integer from 1 to 100.

In some embodiments, the PFPE liquid precursor is synthesized fromhexafluoropropylene oxide or tetrafluoro ethylene oxide as shown inScheme 2.

In some embodiments, the liquid PFPE precursor is synthesized fromhexafluoropropylene oxide or tetrafluoro ethylene oxide as shown inScheme 3.

In some embodiments the liquid PFPE precursor includes a chain extendedmaterial such that two or more chains are linked together before addingpolymerizable groups. Accordingly, in some embodiments, a “linker group”joins two chains to one molecule. In some embodiments, as shown inScheme 4, the linker group joins three or more chains.

In some embodiments, X is selected from the group including, but notlimited to an isocyanate, an acid chloride, an epoxy, and a halogen. Insome embodiments, R is selected from the group including, but notlimited to an acrylate, a methacrylate, a styrene, an epoxy, acarboxylic, an anhydride, a maleimide, an isocyanate, an olefinic, andan amine. In some embodiments, the circle represents any multifunctionalmolecule. In some embodiments, the multifunctional molecule includes acyclic molecule. PFPE refers to any PFPE material provided herein.

In some embodiments, the liquid PFPE precursor includes a hyperbranchedpolymer as provided in Scheme 5, wherein PFPE refers to any PFPEmaterial provided herein.

In some embodiments, the liquid PFPE material includes anend-functionalized material selected from the group including, but notlimited to:

In some embodiments the PFPE liquid precursor is encapped with an epoxymoiety that can be photocured using a photoacid generator. Photoacidgenerators suitable for use in the presently disclosed subject matterinclude, but are not limited to: bis(4-tert-butylphenyl)iodoniump-toluenesulfonate, bis(4-tert-butylphenyl)iodonium triflate,(4-bromophenyl)diphenylsulfonium triflate,(tert-butoxycarbonylmethoxynaphthyl)-diphenylsulfonium triflate,(tent-butoxycarbonylmethoxyphenyl)diphenylsulfonium triflate,(4-tert-butylphenyl)diphenylsulfonium triflate,(4-chlorophenyl)diphenylsulfonium triflate,diphenyliodonium-9,10-dimethoxyanthracene-2-sulfonate, diphenyliodoniumhexafluorophosphate, diphenyliodonium nitrate, diphenyliodoniumperfluoro-1-butanesulfonate, diphenyliodonium p-toluenesulfonate,diphenyliodonium triflate, (4-fluorophenyl)diphenylsulfonium triflate,N-hydroxynaphthalimide triflate,N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate,N-hydroxyphthalimide triflate,[4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium hexafluoroantimonate,(4-iodophenyl)diphenylsulfonium triflate,(4-methoxyphenyl)diphenylsulfonium triflate,2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,(4-methylphenyl)diphenylsulfonium triflate, (4-methylthiophenyl)methylphenyl sulfonium triflate, 2-naphthyl diphenylsulfonium triflate,(4-phenoxyphenyl)diphenylsulfonium triflate,(4-phenylthiophenyl)diphenylsulfonium triflate, thiobis(triphenylsulfonium hexafluorophosphate), triarylsulfonium hexafluoroantimonatesalts, triarylsulfonium hexafluorophosphate salts, triphenylsulfoniumperfluoro-1-butanesulfonate, triphenylsulfonium triflate,tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate, andtris(4-tert-butylphenyl)sulfonium triflate.

In some embodiments the liquid PFPE precursor cures into a highly UVand/or highly visible light transparent elastomer. In some embodimentsthe liquid PFPE precursor cures into an elastomer that is highlypermeable to oxygen, carbon dioxide, and nitrogen, a property that canfacilitate maintaining the viability of biological fluids/cells disposedtherein. In some embodiments, additives are added or layers are createdto enhance the barrier properties of the articles to molecules, such asoxygen, carbon dioxide, nitrogen, dyes, reagents, and the like.

In some embodiments, the material suitable for use with the presentlydisclosed subject matter includes a silicone material having afluoroalkyl functionalized polydimethylsiloxane (PDMS) having thefollowing structure:

wherein:

R is selected from the group including, but not limited to an acrylate,a methacrylate, and a vinyl group;

R_(f) includes a fluoroalkyl chain; and

n is an integer from 1 to 100,000.

In some embodiments, the material suitable for use with the presentlydisclosed subject matter includes a styrenic material having afluorinated styrene monomer selected from the group including, but notlimited to:

wherein R_(f) includes a fluoroalkyl chain.

In some embodiments, the material suitable for use with the presentlydisclosed subject matter includes an acrylate material having afluorinated acrylate or a fluorinated methacrylate having the followingstructure:

wherein:

R is selected from the group including, but not limited to H, alkyl,substituted alkyl, aryl, and substituted aryl; and

R_(f) includes a fluoroalkyl chain with a —CH₂— or a —CH₂—CH₂— spacerbetween a perfluoroalkyl chain and the ester linkage. In someembodiments, the perfluoroalkyl group has hydrogen substituents.

In some embodiments, the material suitable for use with the presentlydisclosed subject matter includes a triazine fluoropolymer having afluorinated monomer.

In some embodiments, the fluorinated monomer or fluorinated oligomerthat can be polymerized or crosslinked by a metathesis polymerizationreaction includes a functionalized olefin. In some embodiments, thefunctionalized olefin includes a functionalized cyclic olefin.

According to an alternative embodiment, the PFPE material includes aurethane block as described and shown in the following structuresprovided in Scheme 6:

According to an embodiment of the present invention, PFPE urethanetetrafunctional methacrylate materials such as the above described canbe used as the materials and methods of the present invention or can beused in combination with other materials and methods described herein,as will be appreciated by one of ordinary skill in the art.

According to this scheme, part A is a UV curable precursor and parts Band C make up a thermally curable component of the urethane system. Thefourth component, part D, is an end-capped precursor, (e.g., styreneend-capped liquid precursor). According to some embodiments, part Dreacts with latent methacrylate, acrylate, or styrene groups containedin a base material, thereby adding chemical compatibility or a surfacepassivation to the base material and increasing the functionality of thebase material.

II.C. Fluoroolefin-based Materials

Further, in some embodiments, the materials used herein are selectedfrom highly fluorinated fluoroelastomers, e.g., fluoroelastomers havingat least fifty-eight weight percent fluorine, as described in U.S. Pat.No. 6,512,063 to Tang, which is incorporated herein by reference in itsentirety. Such fluoroelastomers can be partially fluorinated orperfluorinated and can contain between 25 to 70 weight percent, based onthe weight of the fluoroelastomer, of copolymerized units of a firstmonomer, e.g., vinylidene fluoride (VF₂) or tetrafluoroethylene (TFE).The remaining units of the fluoroelastomers include one or moreadditional copolymerized monomers, that are different from the firstmonomer, and are selected from the group including, but not limited tofluorine-containing olefins, fluorine containing vinyl ethers,hydrocarbon olefins, and combinations thereof.

These fluoroelastomers include VITON® (DuPont Dow Elastomers,Wilmington, Del., United States of America) and Kel-F type polymers, asdescribed in U.S. Pat. No. 6,408,878 to Unger et al. These commerciallyavailable polymers, however, have Mooney viscosities ranging from about40 to 65 (ML 1+10 at 121° C.) giving them a tacky, gum-like viscosity.When cured, they become a stiff, opaque solid. As currently available,VITON® and Kel-F have limited utility for micro-scale molding. Curablespecies of similar compositions, but having lower viscosity and greateroptical clarity, is needed in the art for the applications describedherein. A lower viscosity (e.g., 2 to 32 (ML 1+10 at 121° C.)) or morepreferably as low as 80 to 2000 cSt at 20° C., composition yields apourable liquid with a more efficient cure.

More particularly, the fluorine-containing olefins include, but are notlimited to, vinylidine fluoride, hexafluoropropylene (HFP),tetrafluoroethylene (TFE), 1,2,3,3,3-pentafluoropropene (1-HPFP),chlorotrifluoroethylene (CTFE) and vinyl fluoride.

The fluorine-containing vinyl ethers include, but are not limited toperfluoro(alkyl vinyl)ethers (PAVEs). More particularly, perfluoro(alkylvinyl)ethers for use as monomers include perfluoro(alkyl vinyl)ethers ofthe following formula:CF₂═CFO(R_(f)O)_(n)(R_(f)O)_(m)R_(f)wherein each R_(f) is independently a linear or branched C₁-C₆perfluoroalkylene group, and m and n are each independently an integerfrom 0 to 10.

In some embodiments, the perfluoro(alkyl vinyl)ether includes a monomerof the following formula:CF₂═CFO(CF₂CFXO)_(n)R_(f)wherein X is F or CF₃, n is an integer from 0 to 5, and R_(f) is alinear or branched C₁-C₆ perfluoroalkylene group. In some embodiments, nis 0 or 1 and R_(f) includes 1 to 3 carbon atoms. Representativeexamples of such perfluoro(alkyl vinyl)ethers include perfluoro(methylvinyl)ether (PMVE) and perfluoro(propyl vinyl)ether (PPVE). In someembodiments, the perfluoro(alkyl vinyl)ether includes a monomer of thefollowing formula:CF₂═CFORCF₂)_(m)CF₂CFZO)_(n)R_(f)wherein R_(f) is a perfluoroalkyl group having 1-6 carbon atoms, m is aninteger from 0 or 1, n is an integer from 0 to 5, and Z is F or CF₃. Insome embodiments, R_(f) is C₃F₇, m is 0, and n is 1.

In some embodiments, the perfluoro(alkyl vinyl)ether monomers includecompounds of the formula:CF₂═CFO[(CF₂CF{CF₃}O)_(n)(CF₂CF₂CF₂O)_(m)(CF₂)_(p)]C_(x)F_(2x+1)wherein m and n each integers independently from 0 to 10, p is aninteger from 0 to 3, and x is an integer from 1 to 5. In someembodiments, n is 0 or 1, m is 0 or 1, and x is

Other examples of useful perfluoro(alkyl vinyl ethers) include:CF₂═CFOCF₂CF(CF₃)0(CF₂O)_(m)C_(n)F_(2n+1)wherein n is an integer from 1 to 5, m is an integer from 1 to 3. Insome embodiments, n is 1.

In embodiments wherein copolymerized units of a perfluoro(alkylvinyl)ether (PAVE) are present in the presently describedfluoroelastomers, the PAVE content generally ranges from 25 to 75 weightpercent, based on the total weight of the fluoroelastomer. If the PAVEis perfluoro(methyl vinyl)ether (PMVE), then the fluoroelastomercontains between 30 and 55 wt. % copolymerized PMVE units.

Hydrocarbon olefins useful in the presently described fluoroelastomersinclude, but are not limited to ethylene (E) and propylene (P). Inembodiments wherein copolymerized units of a hydrocarbon olefin arepresent in the presently described fluoroelastomers, the hydrocarbonolefin content is generally 4 to 30 weight percent.

Further, the presently described fluoroelastomers can, in someembodiments, include units of one or more cure site monomers. Examplesof suitable cure site monomers include: i) bromine-containing olefins;ii) iodine-containing olefins; iii) bromine-containing vinyl ethers; iv)iodine-containing vinyl ethers; v) fluorine-containing olefins having anitrile group; yl) fluorine-containing vinyl ethers having a nitrilegroup; vii) 1,1,3,3,3-pentafluoropropene (2-HPFP); viii)perfluoro(2-phenoxypropyl vinyl)ether; and ix) non-conjugated dienes.

In certain embodiments, the brominated cure site monomers can containother halogens, preferably fluorine. Examples of brominated olefin curesite monomers are CF₂═CFOCF₂CF₂CF₂OCF₂CF₂Br; bromotrifluoroethylene;4-bromo-3,3,4,4-tetrafluorobutene-1 (BTFB); and others such as vinylbromide, 1-bromo-2,2-difluoroethylene; perfluoroallyl bromide;4-bromo-1,1,2-trifluorobutene-1; 4-bromo-1,1,3,3,4,4,-hexafluorobutene;4-bromo-3-chloro-1,1,3,4,4-pentafluorobutene;6-bromo-5,5,6,6-tetrafluorohexene; 4-bromoperfluorobutene-1 and3,3-difluoroallyl bromide. Brominated vinyl ether cure site monomersinclude 2-bromo-perfluoroethyl perfluorovinyl ether and fluorinatedcompounds of the class CF₂Br—R_(f)—O—CF═CF₂ (wherein R_(f) is aperfluoroalkylene group), such as CF₂BrCF₂O—CF═CF₂, and fluorovinylethers of the class ROCF═CFBr or ROCBr=CF₂ (wherein R is a lower alkylgroup or fluoroalkyl group), such as CH₃OCF═CFBr or CF₃CH₂OCF═CFBr.

Suitable iodinated cure site monomers include iodinated olefins of theformula: CHR═CH—Z—CH₂CHR—I, wherein R is —H or —CH₃; Z is a C₁ to C₁₈(per)fluoroalkylene radical, linear or branched, optionally containingone or more ether oxygen atoms, or a (per)fluoropolyoxyalkylene radicalas disclosed in U.S. Pat. No. 5,674,959. Other examples of usefuliodinated cure site monomers are unsaturated ethers of the formula:I(CH₂CF₂CF₂)_(n)OCF═CF₂ and ICH₂CF₂O[CF(CF₃)CF₂O]_(n)CF═CF₂, and thelike, wherein n is an integer from 1 to 3, such as disclosed in U.S.Pat. No. 5,717,036. In addition, suitable iodinated cure site monomersincluding iodoethylene, 4-iodo-3,3,4,4-tetrafluorobutene-1 (ITFB);3-chloro-4-iodo-3,4,4-trifluorobutene;2-iodo-1,1,2,2-tetrafluoro-1-(vinyloxy)ethane;2-iodo-1-(perfluorovinyloxy)-1,1,2,2-tetrafluoroethylene;1,1,2,3,3,3-hexafluoro-2-iodo-1-(perfluorovinyloxy)propane; 2-iodoethylvinyl ether; 3,3,4,5,5,5-hexafluoro-4-iodopentene; andiodotrifluoroethylene are disclosed in U.S. Pat. No. 4,694,045. Allyliodide and 2-iodo-perfluoroethyl perfluorovinyl ether also are usefulcure site monomers.

Useful nitrile-containing cure site monomers include, but are notlimited to those of the formulas shown below:CF₂═CF—O(CF₂)_(n)CN

wherein n is an integer from 2 to 12. In some embodiments, n is aninteger from 2 to 6.CF₂═CF—O[CF₂—CF(CF)—O]_(n)—CF₂CF(CF₃)—CNwherein n is an integer from 0 to 4. In some embodiments, n is aninteger from 0 to 2.CF₂═CF—[OCF₂CF(CF₃)]_(x)—O—(CF₂)_(n)—CNwherein x is 1 or 2, and n is an integer from 1 to 4; andCF₂═CF—O—(CF₂)_(n)—O—CF(CF₃)—CNwherein n is an integer from 2 to 4. In some embodiments, the cure sitemonomers are perfluorinated polyethers having a nitrile group and atrifluorovinyl ether group.

In some embodiments, the cure site monomer is:CF₂═CFOCF₂CF(CF₃)OCF₂CF₂CNi.e., perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene) or 8-CNVE.

Examples of non-conjugated diene cure site monomers include, but are notlimited to 1,4-pentadiene; 1,5-hexadiene; 1,7-octadiene;3,3,4,4-tetrafluoro-1,5-hexadiene; and others, such as those disclosedin Canadian Patent No. 2,067,891 and European Patent No. 0784064A1. Asuitable triene is 8-methyl-4-ethylidene-1,7-octadiene.

In embodiments wherein the fluoroelastomer will be cured with peroxide,the cure site monomer is preferably selected from the group including,but not limited to 4-bromo-3,3,4,4-tetrafluorobutene-1 (BTFB);4-iodo-3,3,4,4-tetrafluorobutene-1 (ITFB); allyl iodide;bromotrifluoroethylene and 8-CNVE. In embodiments wherein thefluoroelastomer will be cured with a polyol, 2-HPFP orperfluoro(2-phenoxypropyl vinyl) ether is the preferred cure sitemonomer. In embodiments wherein the fluoroelastomer will be cured with atetraamine, bis(aminophenol) or bis(thioaminophenol), 8-CNVE is thepreferred cure site monomer.

Units of cure site monomer, when present in the presently disclosedfluoroelastomers, are typically present at a level of 0.05-10 wt. %(based on the total weight of fluoroelastomer), preferably 0.05-5 wt. %and most preferably between 0.05 and 3 wt. %.

Fluoroelastomers which can be used in the presently disclosed subjectmatter include, but are not limited to, those having at least 58 wt. %fluorine and having copolymerized units of i) vinylidene fluoride andhexafluoropropylene; ii) vinylidene fluoride, hexafluoropropylene andtetrafluoroethylene; iii) vinylidene fluoride, hexafluoropropylene,tetrafluoroethylene and 4-bromo-3,3,4,4-tetrafluorobutene-1; iv)vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene and4-iodo-3,3,4,4-tetrafluorobutene-1; v) vinylidene fluoride,perfluoro(methyl vinyl)ether, tetrafluoroethylene and4-bromo-3,3,4,4-tetrafluorobutene-1; yl) vinylidene fluoride,perfluoro(methyl vinyl)ether, tetrafluoroethylene and4-iodo-3,3,4,4-tetrafluorobutene-1; vii) vinylidene fluoride,perfluoro(methyl vinyl)ether, tetrafluoroethylene and1,1,3,3,3-pentafluoropropene; viii) tetrafluoroethylene,perfluoro(methyl vinyl)ether and ethylene; ix) tetrafluoroethylene,perfluoro(methyl vinyl)ether, ethylene and4-bromo-3,3,4,4-tetrafluorobutene-1; x) tetrafluoroethylene,perfluoro(methyl vinyl)ether, ethylene and4-iodo-3,3,4,4-tetrafluorobutene-1; xi) tetrafluoroethylene, propyleneand vinylidene fluoride; xii) tetrafluoroethylene and perfluoro(methylvinyl)ether; xiii) tetrafluoroethylene, perfluoro(methyl vinyl)ether andperfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene); xiv)tetrafluoroethylene, perfluoro(methyl vinyl)ether and4-bromo-3,3,4,4-tetrafluorobutene-1; xv) tetrafluoroethylene,perfluoro(methyl vinyl)ether and 4-iodo-3,3,4,4-tetrafluorobutene-1; andxvi) tetrafluoroethylene, perfluoro(methyl vinyl) ether andperfluoro(2-phenoxypropyl vinyl)ether.

Additionally, iodine-containing endgroups, bromine-containing endgroupsor combinations thereof can optionally be present at one or both of thefluoroelastomer polymer chain ends as a result of the use of chaintransfer or molecular weight regulating agents during preparation of thefluoroelastomers. The amount of chain transfer agent, when employed, iscalculated to result in an iodine or bromine level in thefluoroelastomer in the range of 0.005-5 wt. %, preferably 0.05-3 wt. %.

Examples of chain transfer agents include iodine-containing compoundsthat result in incorporation of bound iodine at one or both ends of thepolymer molecules. Methylene iodide; 1,4-diiodoperfluoro-n-butane; and1,6-diiodo-3,3,4,4-tetrafluorohexane are representative of such agents.Other iodinated chain transfer agents include1,3-diiodoperfluoropropane; 1,6-diiodoperfluorohexane;1,3-diiodo-2-chloroperfluoropropane;1,2-di(iododifluoromethyl)perfluorocyclobutane; monoiodoperfluoroethane;monoiodoperfluorobutane; 2-iodo-1-hydroperfluoroethane, and the like.Also included are the cyano-iodine chain transfer agents disclosedEuropean Patent No. 0868447A1. Particularly preferred are diiodinatedchain transfer agents.

Examples of brominated chain transfer agents include1-bromo-2-iodoperfluoroethane; 1-bromo-3-iodoperfluoropropane;1-iodo-2-bromo-1,1-difluoroethane and others such as disclosed in U.S.Pat. No. 5,151,492.

Other chain transfer agents suitable for use include those disclosed inU.S. Pat. No. 3,707,529. Examples of such agents include isopropanol,diethylmalonate, ethyl acetate, carbon tetrachloride, acetone anddodecyl mercaptan.

II.D. Dual Photo-curable and Thermal-curable Materials

According to other embodiments of the present invention, a dual curematerial includes one or more of a photo-curable constituent and athermal-curable constituent. In one embodiment, the photo-curableconstituent is independent from the thermal-curable constituent suchthat the material can undergo multiple cures. A material having theability to undergo multiple cures is useful, for example, in forminglayered articles or in connecting or attaching articles to otherarticles or portions or components of articles to other portions orcomponents of articles. For example, a liquid material havingphotocurable and thermal-curable constituents can undergo a first cureto form a first article through, for example, a photocuring process or athermal curing process. Then the photocured or thermal cured firstarticle can be adhered to a second article of the same material or anymaterial similar thereto that will thermally cure or photocure and bindto the material of the first article. By positioning the first articleand second article adjacent one another and subjecting the first andsecond articles to a thermal curing or photocuring, whichever componentthat was not activated on the first curing. Thereafter, either thethermal cure constituents of the first article that were leftun-activated by the photocuring process or the photocure constituents ofthe first article that were left un-activated by the first thermalcuring, will be activated and bind the second article. Thereby, thefirst and second articles become adhered together. It will beappreciated by one of ordinary skill in the art that the order of curingprocesses is independent and a thermal-curing could occur first followedby a photocuring or a photocuring could occur first followed by athermal curing.

According to yet another embodiment, dual cure materials can includemultiple thermo-curable constituents included in the material such thatthe material can be subjected to multiple independent thermal-cures. Forexample, the multiple thermal-curable constituents can have differentactivation temperature ranges such that the material can undergo a firstthermal-cure at a first temperature range and a second thermal-cure at asecond temperature range. Accordingly, the material can be adhered tomultiple other materials through different thermal-cures, thereby,forming a multiple laminate layer article.

According to another embodiment, dual cure materials can includematerials having multiple photo curable constituents that can betriggered at different wavelengths. For example, a first photo curableconstituent can be triggered at a fisrt applied wavelength and suchwavelength can leave a second photo curable constituent available foractivation at a second wavelength.

Examples of chemical groups which would be suitable end-capping agentsfor a UV curable component include: methacrylates, acrylates, styrenics,epoxides, cyclobutanes and other 2+2 cycloadditions, combinationsthereof, and the like. Examples of chemical group pairs which aresuitable to endcap a thermally curable component include: epoxy/amine,epoxy/hydroxyl, carboxylic acid/amine, carboxylic acid/hydroxyl,ester/amine, ester/hydroxyl, amine/anhydride, acid halide/hydroxyl, acidhalide/amine, amine/halide, hydroxyl/halide, hydroxyl/chlorosilane,azide/acetylene and other so-called “click chemistry” reactions, andmetathesis reactions involving the use of Grubb's-type catalysts,combinations thereof, and the like.

The presently disclosed methods for the adhesion of multiple layers of aarticle to one another or to a separate surface can be applied toPFPE-based materials, as well as a variety of other materials, includingPDMS and other liquid-like polymers. Examples of liquid-like polymericmaterials that are suitable for use in the presently disclosed adhesionmethods include, but are not limited to, PDMS, poly(tetramethyleneoxide), poly(ethylene oxide), poly(oxetanes), polyisoprene,polybutadiene, and fluoroolefin-based fluoroelastomers, such as thoseavailable under the registered trademarks VITON® AND KALREZ®.

Accordingly, the presently disclosed methods can be used to adherelayers of different polymeric materials together to form articles, suchas laminate moldes, and the like.

II.E. Silicone Based Materials

According to alternate embodiments, novel silicone based materialsinclude photocurable and thermal-curable components. In such alternateembodiments, silicone based materials can include one or morephoto-curable and thermal-curable components such that the siliconebased material has a dual curing capability as described herein.Silicone based materials compatible with the present invention aredescribed herein and throughout the reference materials incorporated byreference into this application.

II.F. Phosphazene-Containing Polymers

According to some embodiments, articles and methods disclosed herein canbe formed with materials that include phosphazene-containing polymershaving the following structure. According to these embodiments, R, inthe structure below, can be a fluorine-containing alkyl chain. Examplesof such fluorine-containing alkyl chains can be found in Langmuir, 2005,21, 11604, the disclosure of which is incorporated herein by referencein its entirety. The articles disclosed in this application can beformed from phosphazene-containing polymers or from PFPE in combinationwith phosphazene-containing polymers.

II.G. Materials End-capped with an aryl trifluorovinyl ether (TVE)

In some embodiments, articles and methods disclosed herein can be formedwith materials that include materials end-capped with one or more aryltrifluorovinyl ether (TVE) group, as shown in the structure below.Examples of materials end-capped with a TVE group can be found inMacromolecules, 2003, 36, 9000, which is incorporated herein byreference in its entirety. These structures react in a 2+2 addition atabout 150° C. to form perfluorocyclobutyl moieties. In some embodiments,Rf can be a PFPE chain. In some embodiments three or more TVE groups arepresent on a 3-armed PFPE polymer such that the material crosslinks intoa network.

II.H. Sodium Naphthalene Etchant

In some embodiments a sodium naphthalene etchant, such as commerciallyavailable TETRAETCH™, is contacted with a layer of a fluoropolymerarticle, such as an article disclosed herein. In other embodiments, asodium naphthalene etchant is contacted with a layer of a PFPE-basedarticle, such as laminate articles disclosed herein. According to suchembodiments, the etch reacts with C—F bonds in the polymer of thearticle forming functional groups along a surface of the article. Insome embodiments, these functional groups can then be reacted withmodalities on other layers, on a silicon surface, on a glass surface, onpolymer surfaces, combinations thereof, or the like, thereby forming anadhesive bond. In some embodiments, such adhesive bonds available on thesurface of articles disclosed herein, such as laminate mold articles,can increase adhesion between two articles, layers of an article,combinations thereof, or the like. Increasing the bonding strengthbetween layers of a laminate mold can increase the functionality of thearticle, for example, by increasing the binding strength betweenlaminate layers.

II.I. Trifunctional PFPE precursor

According to some embodiments, a trifunctional PFPE precursor can beused to fabricate articles disclosed herein, such as laminate moldarticles. The trifunctional PFPE precursor disclosed herein can increasethe functionality of an overall article by increasing the number offunctional groups that can be added to the material. Moreover, thetrifunctional PFPE precursor can provide for increased cross-linkingcapabilities of the material. According to such embodiments, articlescan be synthesized by the following reaction scheme.

In further embodiments, a trifunctional PFPE precursor for thefabrication of articles, such as for example laminate articles disclosedherein, is synthesized by the following reaction scheme.

II.J. Fluoroalkyliodide Precursors for Generating Fluoropolymers and/orPFPE's

In some embodiments, functional PFPEs or other fluoropolymers can begenerated using fluoroalkyliodide precursors. According to suchembodiments, such materials can be modified by insertion of ethylene andthen transformed into a host of common functionalities including but notlimited to: silanes, Gringard reagents, alcohols, cyano, thiol,epoxides, amines, and carboxylic acids.

II.K. Diepoxy Materials

According to some embodiments, one or more of the PFPE precursors usefulfor fabricating articles disclose herein, such as laminate articles forexample, contains diepoxy materials. The diepoxy materials can besynthesized by reaction of PFPE diols with epichlorohydrin according tothe reaction scheme below.

II.L. Encapped PFPE Chains with Cycloaliphatic Epoxides

In some embodiments, PFPE chains can be encapped with cycloaliphaticepoxides moeites such as cyclohexane epoxides, cyclopentane epoxides,combinations thereof, or the like. In some embodiments, the PFPE diepoxyis a chain-extending material having the structure below synthesized byvarying the ratio of diol to epichlorohydrin during the synthesis.Examples of some synthesis procedures are described by Tonelli et al. inJournal of Polymer Science: Part A: Polymer Chemistry 1996, Vol 34,3263, which is incorporated herein by reference in its entirety.Utilizing this method, the mechanical properties of the cured materialcan be tuned to predetermined standards.

In further embodiments, the secondary alcohol formed in this reactioncan be used to attach further functional groups. An example of this isshown below whereby the secondary alcohol is reacted with2-isocyanatoethyl methacrylate to yield a material with species reactivetowards both free radical and cationic curing. Functional groups such asin this example can be utilized to bond surfaces together, such as forexample, layers of PFPE material in laminate molds.

II.M. PFPE Diepoxy Cured with Diamines

In some embodiments, PFPE diepoxy can be cured with traditionaldiamines, including but not limited to, 1,6 hexanediamine; isophoronediamine; 1,2 ethanediamine; combinations thereof; and the like.According to some embodiments the diepoxy can be cured with imidazolecompounds including those with the following or related structures whereR1, R2, and R3 can be a hydrogen atom or other alkyl substituents suchas methyl, ethyl, propyl, butyl, fluoroalkyl compounds, combinationsthereof, and the like. According to some embodiments, the imidazoleagent is added to the PFPE diepoxy in concentrations on the order ofbetween about 1-25 mol % in relation to the epoxy content. In someembodiments the PFPE diepoxy containing an imidazole catalyst is thethermal part of a two cure system, such as described elsewhere herein.

II.N. PFPE Cured with Photoacid Generators

In some embodiments, a PFPE diepoxy can be cured through the use ofphotoacid generators (PAGs), The PAGs are dissolved in the PFPE materialin concentrations ranging from between about 1 to about 5 mol % relativeto epoxy groups and cured by exposure to UV light. Specifically, forexample, these photoacid generators can posses the following structure(Rhodorsil™) 2074 (Rhodia, Inc):

In other embodiments, the photoacid generator can be, for example,Cyracure™ (Dow Corning) possessing the following structure:

II.O. pfpe Diol Containing a Poly(Ethylene Glycol)

In some embodiments, commercially available PFPE diols containing anumber of poly(ethylene glycol) units can be used as the material forfabrication of a article, such as laminate articles. In otherembodiments, the commercially available PFPE diol containing a givennumber f poly(ethylene glycol) units is used in combination with othermaterials disclosed herein. Such materials can be useful for dissolvingthe above described photoinitiators into the PFPE diepoxy and can alsobe helpful in tuning mechanical properties of the material as the PFPEdiol containing a poly(ethylene glycol) unit can react with propagatingepoxy units and can be incorporated into the final network.

II.P. PFPE Diols and/or Polyols Mixed with a PFPE Diepoxy

In further embodiments, commercially available PFPE diols and/or polyolscan be mixed with a PFPE diepoxy compound to tune mechanical propertiesby incorporating into the propagating epoxy network during curing.

II.Q. PFPE Epoxy-Containing a Pag Blended with a Photoinitiator

In some embodiments, a PFPE epoxy-containing a PAG can be blended withbetween about 1 and about 5 mole % of a free radical photoinitiator suchas, for example, 2,2-dimethoxyacetophenone, 1-hydroxy cyclohexyl phenylketone, diethoxyacetophenone, combinations thereof, or the like. Thesematerials, when blended with a PAG, form reactive cationic species whichare the product of oxidation by the PAG when the free-radical initiatorsare activated with UV light, as partially described by Crivello et al.Macromolecules 2005, 38, 3584, which is incorporated herein by referencein its entirety. Such cationic species can be capable of initiatingepoxy polymerization and/or curing. The use of this method allows thePFPE diepoxy to be cured at a variety of different wavelengths.

II.R. PFPE Diepoxy Containing a Photoacid Generator and Blended with aPFPE Dimethacrylate

In some embodiments, a PFPE diepoxy material containing a photoacidgenerator can be blended with a PFPE dimethacrylate material containinga free radical photoinitiator and possessing the following structure:

The blended material includes a dual cure material which can be cured atone wavelength, for example, curing the dimethacrylate at 365 nm, andthen bonded to other layers of material through activating the curing ofthe second diepoxy material at another wavelength, such as for example254 nm. In this manner, multiple layers of patterned PFPE materials canbe bonded and adhered to other substrates such as glass, silicon, otherpolymeric materials, combinations thereof, and the like at differentstages of fabrication of an overall article.

II.S. Other Materials

According to alternative embodiments, the following materials can beutilized alone, in connection with other materials disclosed herein, ormodified by other materials disclosed here and applied to the methodsdisclosed herein to fabricate the articles disclosed herein. Moreover,end-groups disclosed herein and disclosed in U.S. Pat. Nos. 3,810,874;and 4,818,801, each of which is incorporated herein by referenceincluding all references cited therein.

II.S.1 Diurethane Methacrylate

In some embodiments, the material is or includes diurethane methacrylatehaving a modulus of about 4.0 MPa and is UV curable with the followingstructure:

II.S.ii Chain-Extended Diurethane Methacrylate

In some embodiments, the material is or includes a chain extendeddiurethane methacrylate, wherein chain extension before end-cappingincreases molecular weight between crosslinks, a modulus ofapproximately 2.0 MPa, and is UV curable, having the followingstructure:

II.S.iii Diisocyanate

In some embodiments, the material is typically one component of atwo-component thermally curable system; may be cured by itself through amoisture cure technique; and has the following structure:

II.S.iv Chain Extended Diisocyanate

In some embodiments, the material is or includes, one component of a twocomponent thermally curable system; chain extended by linking severalPFPE chains together; may be cured by itself through a moisture cure;and includes the following structure:

II.S.v Blocked Diisocyanate

In some embodiments, the material is or includes: one component of a twocomponent thermally curable system; and includes the followingstructure:

II.S.vi PFPE Three-Armed Triol

In some embodiments, the material is or includes a PFPE triol as onecomponent of a two-component thermally curable urethane system; includesthe benefits of being highly miscible with other PFPE compositions; andincludes the following structure:

II.S.vii PFPE DiStyrene

In some embodiments, the material is or includes PFPE distyrene materialthat is UV curable, highly chemically stable, is useful in makinglaminate coatings with other compositions, and includes the followingstructure:

II.S.viii Diepoxy

In some embodiments, the material can be UV cured; can be thermallycured by itself using imidazoles; can also be thermally cured in atwo-component diamine system; is highly Chemically stable; and includesthe following structure:

II.S.ix Diamine

In some embodiments, the material can be thermally cured in atwo-component diamine system; has functionality of 6 (3 amines availableon each end); is highly chemically stable; and includes the followingstructure:

II.S.x Thermally Cured PU-Tetrol

In some embodiments, the material can be thermally cured in atwo-component system, such as for example mixed in a 2:1 molar ratio atabout 100-about 130 degrees C.; forms tough, mechanically stablenetwork; the cured network is slightly cloudy due to immiscibility oftetrol; and includes the following structure:

II.S.xi Thermally Cured PU-Triol

In some embodiments, the material can be thermally cured in atwo-component system, such as for example mixed in a 3:2 molar ratio, atabout 100-about 130 degrees C.; forms tough, mechanically stablenetwork; where the cured network is clear and colorless; and includesthe following structure:

II.S.xii Thermally Cured Epoxy

In some embodiments, the material can be thermally cured in atwo-component system, such as for example mixed in a 3:1 molar ratio, atabout 100-about 130 degrees C.; forms mechanically stable network; wherethe cured network is clear and colorless; has high chemical stability;and includes the following structure:

II.S.xiii UV-Cured Epoxy

In some embodiments, the material is a UV curable composition; includesZDOL TX used to solubilize PAG; where the cured network is clear andyellow; has high chemical stability; and includes the followingstructure:

II.S.ixv UV-Thermal Dual Cure

In some embodiments, the material can be mixed in a 2:1 ratio (UV tothermal); forms cloudy network (tetrol); has a high viscosity; forms avery strong adhesion; has very good mechanical properties; and includesthe following structure:

II.S.xv Orthogonal Cure with Triol

In some embodiments, the material can be mixed in a 2:1 ratio (UV tothermal); forms clear and colorless network; has a high viscosity; formsvery strong adhesion; includes very good mechanical properties; andincludes the following structure:

II.S.xvi UV Orthogonol System

In some embodiments, the material includes ZDOL-TX, which can be mixedin a 1:1 ratio (epoxy to methacrylate); forms clear and yellow network;has strong adhesion properties; has good mechanical properties; andincludes the following structure:

II.S.xvii UV with Epoxy Dual Cure

In some embodiments, the material forms slightly yellow network;includes a ratio (2:1 UV to thermal); has good mechanical properties;good adhesion; is highly chemical stability; and includes the followingstructure:

II.S.xviii Orthogonal with Diisocyanate

In some embodiments, the material is one component thermal component(Isocyanate reacts with urethane linkage on urethane dimethacrylate);has good mechanical properties; forms a strong adhesion; cures to clear,slightly yellow network; and includes the following structure:

III. Patterned Laminate Molds Fabricated from the Disclosed Materials

The materials of the present invention can be utilized to form laminatelayers of nano-sized predetermined shape molds and lamination adhesionpromoter tie-layers for fabricating such molds. Referring now to FIG. 1,a general laminate mold 100 of the present invention includes a backinglayer 102 affixed to a patterned mold layer 104 by a tie-layer 106. Incertain embodiments, tie-layer 106 is used to bond mold layer 104 tobacking layer 102. According to some embodiments, patterned mold layer104 includes a patterned surface 108. Mold layer 104 can be made fromthe materials disclosed herein, and combinations thereof. Patterns onpatterned surface 108 can include cavities 110 and land area L thatextends between cavities 110. Patterns on patterned surface 108 can alsoinclude a pitch, such as pitch P, which is generally the distance from afirst edge of one cavity to a first edge of an adjacent cavity includingland area L between the adjacent cavities.

According to some embodiments, laminate mold 100 is fabricated from atwo stage lamination process. Initially, a composition, (e.g. a materialdescribed herein such as a dual-cure composition) includes thestructures shown below in Scheme 1 of Example 1.

micrometers and about 75 micrometers. In other embodiments, thetie-layer 210 is distributed into a layer of between about 10micrometers and about 50 micrometers. In some embodiments, the tie-layer210 is distributed into a layer of between about 15 micrometers andabout 40 micrometers. In some embodiments, the tie-layer 210 isdistributed into a layer of between about 20 micrometers and about 30micrometers. In some embodiments, the tie-layer 210 is distributed intoa layer of between about 10 micrometers and about 35 micrometers. Insome embodiments, the tie-layer 210 is distributed into a layer ofbetween about 10 micrometers and about 25 micrometers. According to someembodiments, the two roll laminator is actuated at a speed of about 5ft/minute. According to another embodiment, the two roll laminator isactuated at a speed of less than about 5 ft/minute. According to otherembodiments, the two roll laminator is actuated at a speed of betweenabout 1 ft/minute and about 10 ft/minute. According to still anotherembodiment, the two roll laminator is actuated at a speed of about 1ft/minute.

After roll laminating polymer sheets 206 and 208 with tie-layer 210distributed therebetween, laminate 214 is cured (e.g., UV cured) to cureor partially cure tie-layer 210. In some embodiments, laminate 214 iscured (e.g., UV cured) in a conveyer system (e.g., UV conveyer system)in which the conveyor is moved at about 8 ft/minute and the UV poweroutput is about 200 Watts/inch. According to such embodiments, laminate214 is positioned approximately 3 inches from the UV source for UVcuring. In some embodiments, following curing, the cured laminate 214 issecondarily cured (e.g., placed in a thermal oven) for curing oftie-layer 210. In some embodiments, thermal oven is set at, andpreheated to, 100° C. and laminate 214 is subjected to the thermalcondition of the thermal oven for about 10 minutes. After laminate 214has been secondarily cured (e.g., thermal cured) polymer sheets 206 and208 are separated. In some embodiments, polymer sheets 206 and 208 areseparated by hand by peeling sheets 206 and 208 apart at a rate of about1 inch per second. In preferred embodiments, tie-layer 210 remainssubstantially entirely on one of the polymer sheets, 206 or 208.

In some embodiments, separately, a UV curable PFPE resin, having aformula shown as Scheme 2 of Example 1, is mixed with 2.0% by weightdiethoxyacetophenone. In some embodiments, the UV curable PFPE resin andthe 2.0% by weight diethoxyacetophenone is mixed by hand for more thanabout 2 minutes at room temperature in a glass vial.

Next, polymer sheet 206 with tie-layer 210 affixed thereto is positionedwith respect to a patterned master 216, as shown in FIG. 3. In someembodiments, patterned master is a silicon wafer master patterned withan array of nano-sized structures having predetermined shapes. In otherembodiments, patterned master 216 includes viruses, nanotubes, ordendrimers on surfaces. In other embodiments, patterned master 216 caninclude anodized alumina templates. In some embodiments, the nano-sizedstructures are 200 nm×200 nm×400 nm cylindrical posts. In otherembodiments, the nano-sized structures are 2 micron×2 micron×0.7 microncuboidal structures protruding from the silicon master.

In other embodiments, the nano-sized structures are 1 micron×1micron×0.7 micron cuboidal structures protruding from the siliconmaster. In other embodiments, the nano-sized structures are 1 microndiameter×0.7 micron height cylindrical post structures protruding fromthe silicon master. In other embodiments, the nano-sized structures are0.9 micron×0.9 micron×0.9 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.9micron×0.9 micron×0.7 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.9micron diameter×0.9 micron height cylindrical structures protruding fromthe silicon master. In other embodiments, the nano-sized structures are0.8 micron×0.8 micron×0.8 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.8micron×0.8 micron×0.6 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.8micron diameter×0.8 micron height cylindrical structures protruding fromthe silicon master. In other embodiments, the nano-sized structures are0.7 micron×0.7 micron×0.7 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.7micron×0.7 micron×0.5 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.7micron diameter×0.7 micron height cylindrical structures protruding fromthe silicon master. In other embodiments, the nano-sized structures are0.6 micron×0.6 micron×0.6 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.6micron×0.6 micron×0.3 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.6micron diameter×0.6 micron height cylindrical structures protruding fromthe silicon master. In other embodiments, the nano-sized structures are0.5 micron×0.5 micron×0.5 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.5micron×0.5 micron×0.2 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.5micron diameter×0.8 micron height cylindrical structures protruding fromthe silicon master. In other embodiments, the nano-sized structures are0.4 micron×0.4 micron×0.4 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.4micron×0.4 micron×0.7 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.4micron diameter×0.4 micron height cylindrical structures protruding fromthe silicon master. In other embodiments, the nano-sized structures are0.3 micron×0.3 micron×0.3 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.3micron×0.3 micron×0.1 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.3micron diameter×0.2 micron height cylindrical structures protruding fromthe silicon master. In other embodiments, the nano-sized structures are0.2 micron×0.2 micron×0.2 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.2micron×0.2 micron×0.05 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.2micron diameter×0.2 micron height cylindrical structures protruding fromthe silicon master. In other embodiments, the nano-sized structures are0.1 micron×0.1 micron×0.1 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.1micron×0.1 micron×0.05 micron cuboidal structures protruding from thesilicon master. In other embodiments, the nano-sized structures are 0.1micron diameter×0.1 micron height cylindrical structures protruding fromthe silicon master.

According to still other embodiments, the nano-sized structures can beless than about 10 nm is a broadest dimension. In other embodiments, thenano-sized structures can be between about 5 nm and about 25 nm. Inother embodiments, the nano-sized structures can be between about 5 nmand about 50 nm. In other embodiments, the nano-sized structures can bebetween about 5 nm and about 75 nm. In other embodiments, the nano-sizedstructures can be between about 5 nm and about 100 nm. In otherembodiments, the nano-sized structures can be between about 5 nm andabout 150 nm. In other embodiments, the nano-sized structures can bebetween about 5 nm and about 200 nm. In other embodiments, thenano-sized structures can be between about 5 nm and about 250 nm. Inother embodiments, the nano-sized structures can be between about 5 nmand about 350 nm. In other embodiments, the nano-sized structures can bebetween about 5 nm and about 500 nm. In other embodiments, thenano-sized structures can be between about 5 nm and about 750 nm. Inother embodiments, the nano-sized structures can be between about 5 nmand about 1 micrometer. In other embodiments, the nano-sized structurescan be between about 5 nm and about 2 micrometers. In other embodiments,the nano-sized structures can be between about 5 nm and about 5micrometers.

Next, polymer sheet 206, having tie-layer 210 positioned adjacent apatterned side of patterned master 216 and the combination is introducedinto nips of a two roll laminator, such as two roll laminator 200described above. After polymer sheet 206 and patterned master 216 areaffixed in rollers 202 and 204, UV curable material 218, such as thatdisclosed herein, is introduced between an interface of patterned master216 and tie-layer 210 of polymer sheet 206. Two roll laminator 200 isthen activated to thereby laminate polymer sheet 206, tie-layer 210, UVcurable material 218, and patterned master 216 together. After thecombination of layers has passed through two roll laminator 200, thecombination laminate is cured (e.g. UV cured) to cure curable material218 into a solidified layer attached to tie-layer 210. According to someembodiments, after patterned master 216 is separated from laminatelayers 206, 210, and 218, the resulting laminate includes a thin layerof curable material 218 adhered to tie-layer 210 which is adhered topolymer sheet 206. Furthermore, curable layer 218 includes an inversereplica of features of patterned master 216, such as cavities 110. Insome embodiments, curable layer 218 is between about 5 microns and about50 microns thick. In some embodiments, curable layer 218 is betweenabout 5 microns and about 30 microns thick. In some embodiments, curablelayer 218 is between about 10 microns and about 25 microns thick. Insome embodiments, curable layer 218 is less than about 75 microns thick.In some embodiments, curable layer 218 is less than about 70 micronsthick. In some embodiments, curable layer 218 is less than about 65microns thick. In some embodiments, curable layer 218 is less than about60 microns thick. In some embodiments, curable layer 218 is less thanabout 55 microns thick. In some embodiments, curable layer 218 is lessthan about 50 microns thick. In some embodiments, curable layer 218 isless than about 45 microns thick. In some embodiments, curable layer 218is less than about 40 microns thick. In some embodiments, curable layer218 is less than about 35 microns thick. In some embodiments, curablelayer 218 is less than about 30 microns thick. In some embodiments,curable layer 218 is less than about 25 microns thick. In someembodiments, curable layer 218 is less than about 20 microns thick. Insome embodiments, curable layer 218 is less than about 15 microns thick.In some embodiments, curable layer 218 is less than about 10 micronsthick. In some embodiments, curable layer 218 is less than about 7microns thick.

In still other embodiments, laminate mold 100 is configured with abacking 102 and a single laminate layer 104 adhered directly to backing102. According to certain embodiments, laminate layer 104 is dual-curematerials disclosed herein, UV-curable materials, thermal curablematerials, disclosed herein. Such laminte molds are fabricated,according to FIG. 3, however, without using tie-layer 210 on backinglayer 206. Accordingly, backing layer 206 and patterned master 216 areconfigured in alignment with each other and with rollers 202 and 204, asdescribed herein. Next, either dual-cure materials described herein,UV-curable materials disclosed herein, or thermal curable materials aredeposited between backing layer 206 and patterned master 216 on an inputside of rollers 202 and 204. Then, when the rollers are activated thedual-cure or UV-curable material is dispersed between backing 206 andpatterned master 216 and conform to a pattern of patterned master 216.Next, the laminate of backing 206, un-cured dual-cure or UV-curablematerial, and patterned master 216 are subjected to a UV-curingtreatment T, as shown in FIG. 4. Following UV-curing, if a UV-curablematerial was used, the patterned master 216 and backing 206 areseparated, as shown in the right side of FIG. 4. However, if a dual-curematerial was utilized, the UV-cured laminate is subjected to a thermalcuring to active the thermal component of the dual-cure. Followingthermal curing, the backing 206 and patterned master 216 is separatedsuch that the dual-cure layer mimics the pattern of patterned master 216and is adhered to backing 206, as shown in FIG. 4.

Referring now to FIG. 5, a laminate mold 500 mimicking patternedstructures of a patterned master 216 are shown. According to FIG. 5, thestructures mimicked are 200 nm diameter cylindrical cavities orcavities, the land area L is roughly 200 nm, and the pitch P is roughly400 nm. FIG. 6 shows a molded material 600 molded from the laminate mold500 of FIG. 5, wherein structures 602 are 200 nm diameter cylindricalposts, land area L is roughly 200 nm, and pitch P is roughly 400 nm.

In some embodiments, cavities 110 can include any structure that isetched onto silicone wafer. In some embodiments, cavities 110 caninclude an array of structures which are a repetitious pattern, a randompattern, and combinations thereof of the same structure or a variety ofstructure sizes and shapes. According to some embodiments, cavities 110have a cross-sectional diameter of less than about 5 micrometers.According to some embodiments, cavities 110 have a cross-sectionaldiameter of less than about 2 micrometers. According to someembodiments, cavities 110 have a cross-sectional diameter of less thanabout 1 micrometer. According to some embodiments, cavities 110 have across-sectional diameter of less than about 500 nm. According to someembodiments, cavities 110 have a cross-sectional diameter of less thanabout 250 nm. According to some embodiments, cavities 110 have across-sectional diameter of less than about 200 nm. According to someembodiments, cavities 110 have a cross-sectional diameter of less thanabout 150 nm. According to some embodiments, cavities 110 have across-sectional diameter of less than about 100 nm. According to someembodiments, cavities 110 have a cross-sectional diameter of less thanabout 75 nm. According to some embodiments, cavities 110 have across-sectional diameter of less than about 50 nm. According to someembodiments, cavities 110 have a cross-sectional diameter of less thanabout 40 nm. According to some embodiments, cavities 110 have across-sectional diameter of less than about 30 nm. According to someembodiments, cavities 110 have a cross-sectional diameter of less thanabout 20 nm. According to some embodiments, cavities 110 have across-sectional diameter of less than about 15 nm. According to someembodiments, cavities 110 have a cross-sectional diameter of less thanabout 10 nm.

According to some embodiments, cavities 110 have a depth of less thanabout 500 nm. According to other embodiments, cavities 110 have a depthof less than about 300 nm. According to some embodiments, cavities 110have a depth of less than about 250 nm. According to some embodiments,cavities 110 have a depth of less than about 150 nm. According to someembodiments, cavities 110 have a depth of less than about 100 nm.According to some embodiments, cavities 110 have a depth of less thanabout 75 nm. According to some embodiments, cavities 110 have a depth ofless than about 50 nm. According to some embodiments, cavities 110 havea depth of less than about 30 nm. According to some embodiments,cavities 110 have a depth of less than about 20 nm. According to someembodiments, cavities 110 have a depth of less than about 15 nm.According to some embodiments, cavities 110 have a depth of less thanabout 10 nm.

According to other embodiments, cavities 110 have a width to depth ratioof between about 1,000:1 and about 100,000:1. According to otherembodiments, cavities 110 have a width to depth ratio of between about1,000:1 and about 10,000:1. According to other embodiments, cavities 110have a width to depth ratio between of about 100:1 and about 1, 000:1.According to other embodiments, cavities 110 have a width to depth ratioof about 1, 000:1. According to other embodiments, cavities 110 have awidth to depth ratio of about 800:1. According to other embodiments,cavities 110 have a width to depth ratio of about 600:1. According toother embodiments, cavities 110 have a width to depth ratio of about500:1. According to other embodiments, cavities 110 have a width todepth ratio of about 400:1. According to other embodiments, cavities 110have a width to depth ratio of about 300:1. According to otherembodiments, cavities 110 have a width to depth ratio of about 200:1.According to other embodiments, cavities 110 have a width to depth ratioof about 100:1. According to other embodiments, cavities 110 have awidth to depth ratio of about 80:1. According to other embodiments,cavities 110 have a width to depth ratio of about 70:1. According toother embodiments, cavities 110 have a width to depth ratio of about50:1. According to other embodiments, cavities 110 have a width to depthratio of about 40:1. According to other embodiments, cavities 110 have awidth to depth ratio of about 30:1. According to other embodiments,cavities 110 have a width to depth ratio of about 20:1. According toother embodiments, cavities 110 have a width to depth ratio of about10:1. According to other embodiments, cavities 110 have a width to depthratio of about 5:1. According to other embodiments, cavities 110 have awidth to depth ratio of about 2:1.

According to some embodiments, a shape of cavities 110 are selected fromthe group of cylindrical, cuboidal, star, arrow, semi-spherical,conical, cresent, viral, cellular, concave disk, and any other shapethat can be etched into a patterned master such as a silicon wafer.

In some embodiments, polymer sheet 206 is a PET sheet having a thicknessof less than about 10 mil. In some embodiments, a PET sheet having atie-layer 210 and a UV curable PFPE layer 218 can have a modulus ofabout 1400 MPa. According to some embodiments, the land area of thelaminate mold is between about 5% and about 99% of the entire surfacearea. According to some embodiments, the land area of the laminate moldis between about 5% and about 90% of the entire surface area. Accordingto some embodiments, the land area of the laminate mold is between about5% and about 80% of the entire surface area. According to someembodiments, the land area of the laminate mold is between about 5% andabout 75% of the entire surface area. According to some embodiments, theland area of the laminate mold is between about 5% and about 60% of theentire surface area. According to some embodiments, the land area of thelaminate mold is between about 5% and about 50% of the entire surfacearea. According to some embodiments, the land area of the laminate moldis between about 5% and about 40% of the entire surface area. Accordingto some embodiments, the land area of the laminate mold is between about5% and about 30% of the entire surface area. According to someembodiments, the land area of the laminate mold is between about 5% andabout 25% of the entire surface area. According to some embodiments, theland area of the laminate mold is between about 5% and about 20% of theentire surface area. According to some embodiments, the land area of thelaminate mold is between about 5% and about 15% of the entire surfacearea. According to some embodiments, the land area of the laminate moldis between about 5% and about 10% of the entire surface area.

According to some embodiments, the dual-cure material and the UV-curablematerial of the laminate molds of the present invention can include thematerials described herein. In some embodiments, the PFPE formulationsdescribed herein are used themselves as the molded layer of thelaminate. In further embodiments molded PFPE layers are adhered tobacking substrates using tie-layers formulated with PFPEs containingvarious functional end groups. In further embodiments the tie-layerincludes a dual-cure mixture of PFPE materials such that one componentis capable of being cured by actinic radiation and another is capable ofbeing cured thermally. In other embodiments, the molded PFPE layeritself may include a dual-cure PFPE formulation.

In some embodiments an additional tie-layer structure is not neededbetween the substrate and the PFPE mold. In further embodiments the PFPEformulation used to fabricate the mold is formulated such that it willadhere to a particular backing material upon curing. In furtherembodiments, the backing material is chemically functionialized toadhere to a particular PFPE mold formulation.

It should be appreciated, however, that the present invention can beembodied in different forms and should not be construed as limited tothe embodiments set forth herein. Unless otherwise defined, alltechnical and scientific terms used herein have the same meaning ascommonly understood by one of ordinary skill in the art to which thispresently described subject matter belongs. All publications, patentapplications, patents, and other references mentioned herein areincorporated herein by reference in their entirety. Throughout thespecification and claims, a given chemical formula or name shallencompass all optical and stereoisomers, as well as racemic mixtureswhere such isomers and mixtures exist.

IV. Examples

The following Examples have been included to provide guidance to one ofordinary skill in the art for practicing representative embodiments ofthe presently disclosed subject matter. In light of the presentdisclosure and the general level of skill in the art, those of skill canappreciate that the following Examples are intended to be exemplary onlyand that numerous changes, modifications, and alterations can beemployed without departing from the scope of the presently disclosedsubject matter.

Example 1

Step 1: To form an adhesion promoter for PFPE molds to PET, a dual-curecomposition of the PFPE structures, shown below in Scheme 1 of Example1, was mixed by hand stir for at least 2 minutes at room temperature ina glass vial. In particular, the dual-cure composition of PFPEstructures includes the structures shown in Scheme 1 with 2.0% by weightdiethoxyacetophenone photoinitiator and 0.1% by weight dibutyltindiacetate catalyst.

Step 2: Two 6″×12″×7 mil sheets of Melinex 453 (Dupont Teijin Films)treated poly(ethylene terephthalate) (PET) (one side treated) wereprovided. The two sheets were then configured with a treated side of onesheet facing an untreated side of the other sheet. The configured sheetswere inserted into a two roll laminator having two 1″ diameter rubbercoated rollers having a length of 8″ with both rubber rollers having ashore hardness value of 85. The rollers were closed, thereby pinchingthe configured sheets at a pressure of 60 psig pneumatically driventogether by two cylinders of 1″ in diameter with approximately 2″ of thePET sheets extending beyond the exit side of the rollers. Approximately2 mL of the dual-cure mixture was placed between the two PET sheets nearthe nip point on the input side of the rollers. The dual-cure wasdeposited in an even bead manner from a syringe having an opening ofabout 1 mm. The two roll laminator was then actuated at a speed of 1ft/minute, driving the configuration through the nips and dispersing thedual-cure mixture between the two PET sheets and sealing the two PETsheets together with a thin film of dual-cure resin in between as shownin FIG. 2. The two roll laminator was stopped prior to the two PETsheets passing completely through the nip point, such that about 1 inchof PET remained above the input side of the rollers.

Step 3: The PET/dual-cure resin/PET laminate was then UV cured in a UVconveyer system (UVPS conveyor system with Mercury arc lamp source modelUVPS6T). The UV conveyor moved at 8 ft/minute with a power output of 200Watts/inch placed approximately 3 inches above the sample. Prior tosubjecting the PET/dual-cure resin/PET laminate to the UV cure, the UVconveyer was allowed to warm-up for about 10 minutes to reach fulloperating potential.

Step 4: Next, the UV-cured PET/dual-cure resin/PET laminate was placedin a thermal oven set at, and preheated to, 100° C. for 10 minutes.Following this, the PET/dual-cure/PET laminate was allowed to cool atroom temperature for 1 minute before the PET sheets were separated byhand by peeling the two PET sheets apart at a rate of about 1 inch persecond. The sheets separated cleanly with the dual-cure resin remainingon the PET non-Melinex 453 side of the laminate and the Melinex 453treated side peeling off free of dual-cure resin.

Step 5: Separately, the UV curable PFPE resin, having the formula belowin Scheme 2 of Example 1, was mixed by hand for about 2 minutes at roomtemperature in a glass vial with 2.0% by weight diethoxyacetophenone.

Step 6: Next, an 8″ silicon wafer master patterned with an array of 200nm×200 nm×400 nm cylindrical posts was configured with the PET/dual-curelaminate sheet, formed in Steps 1-4, such that the dual-cure side wasfacing the patterned side of the wafer. The laminate and the wafer werethen inserted into a two roll laminator having two 1″ diameter rubbercoated rollers 8″ in length with both rubber rollers having a shorehardness value of 85. The rollers were closed, thereby pinching theconfigured sheets at a pressure of 60 psig, pneumaticaly driven by twosteel cylinders of 1″ diameter with 1″ of the layers protruding beyondthe exit side of the rollers. Approximately 1 mL of the UV-curable PFPEcompound, described in Step 5, was evenly placed between thePET/dual-cure sheet and the wafer near the nip point on the inlet sideof the rollers. The UV-curable PFPE was disposed in a bead pattern froma syringe having an opening of about 1 mm. The laminator was thenactuated at a speed of 6 ft/min, laminating the PET/dual cure sheet tothe 8″ patterned wafer with a thin film of UV-curable PFPE distributedin between as shown in FIG. 3. The two roll laminator was then stoppedwhen about 1 inch of the PET/dual-cure laminate/UV-curable PFPE/siliconmaster remained on the inlet side of the rollers. The rollers werecarefully opened to release the PET/dual-cure laminate/UV-curablePFPE/silicon master laminate.

Step 7: The Dual cure sheet/UV-curable PFPE/Silicon wafer laminate wasexposed to UV light through the PET sheet using a floodlamp (Oriel ArcLamp, Mercury-Xenon, model 81172) placed approximately 3 inches from thesample for 1 minute to cure the UV-curable PFPE resin. Prior to exposingthe dual-cure sheet/UV-curable PFPE/silicon wafer laminate to the UVfloodlamp, the UV light source was allowed to warm up for 10 minutes.After exposure for 10 minutes, the light was extinguished and thedual-cure sheet/UV-curable PFPE/silicon wafer laminate was removed.Following removal from the floodlamp, the dual-cure sheet/UV-curablePFPE layer was carefully separated, by hand peeling at about 1 inch persecond from the silicon master. Upon separation, a thin (10-20 micron)PFPE layer was adhered to the dual-cure adhered to the PET and the thinPFPE layer included features of the etched silicon wafers. An example ofthese procedures is shown in FIG. 4.

Step 8: The PFPE mold was inspected after fabrication by scanningelectron microscopy (SEM). FIG. 5 shows a representative image. FIG. 5is an SEM image of a PFPE/PET laminate mold with 200 nm cavities in ahexagonal array.

Step 9: Mechanical Properties of the laminate mold formed in steps 1-7were compared to a 1 mm thick mold made purely from the UV curable PFPEcomposition shown in Scheme 2. The thick mold was formed by castingdirectly onto the silicon master and UV curing under nitrogen for 2minutes using an (ELC-4001 UV flood lamp available from ElectroliteCorp, Bethel, Conn.).

Mold Material Modulus (MPa) UV-curable PFPE (scheme 2) 7 PFPE/PETLaminate 1440

Step 10: The laminate mold formed in Step 7 was configured with a6″×12″×7 mil sheet of Melinex 453 such that the patterned side of themold was facing the treated side of the PET. The sheets were insertedinto a two roll laminator having two 1″ diameter rubber coated rollers6″ in length; one with a shore hardness of 30, and the other with ashore hardness of 70. The pattern on the laminate mold was facing the 30durometer roller. The rollers were closed, thereby pinching theconfigured sheets at a pressure of 40 psig pneumaticaly driven by twosteel cylinders of 1″ diameter with 1 inch of the layers protrudingbeyond the exit side of the rollers. Approximately 1 mL of a UV-curableoptical adhesive, Dymax 1180-M (DYMAX Corp. Torrington, Conn.), wasplaced between the two PET sheets at the nip point on the top of therollers. The laminator was then actuated at a speed of 4.6 ft/min,sealing the two PET sheets together with a thin film of Dymax 1180-Mresin in between.

Step 11: The laminate was UV cured on the conveyer system described withrespect to Step 3, moving at 8 ft/minute with a power output of 200Watts/inch placed approximately 3 inches above the sample. The laminatewas UV cured with the PET backed PFPE mold side toward the UV lamp.

Step 12: The layers were then carefully separated by hand peeling atabout 1 inch per second to reveal a replicate pattern of the originalpatterned silicon master formed in the Dymax 1180-M. The fidelity of thepattern was inspected using SEM. FIG. 6 shows a representative image ofthe replica pattern formed from the laminate mold. FIG. 6 is an SEMimage of a polymer replica on PET of hexagonally packed 200 nm postsformed from a PFPE/PET laminate mold.

Example 2

Step 1: To form an adhesion promoter for PFPE molds to PET, a dual-curecomposition of the PFPE structures, shown in Scheme 1 of Example 1, wasmixed by hand stir for at least 2 minutes at room temperature in a glassvial. In particular, the dual-cure composition of PFPE structuresincludes the structures shown in Scheme 1 of Example 1 with 2.0% byweight diethoxyacetophenone photoinitiator and 0.1% by weight dibutyltindiacetate catalyst.

Step 2: Two 6″×12″×7 mil sheets of Melinex 453 (Dupont Teijin Films)poly(ethylene terephthalate) (PET) were cut. The two sheets were thenconfigured with a treated side of one sheet facing an untreated side ofthe other sheet. The configured sheets were inserted into a two rolllaminator having two different size rollers. One roller is a 16 mmdiameter rubber covered roller 9″ l length with a shore hardness of 30and the other roller is a 30 mm diameter aluminum roller 9″ in length.The rollers were closed, thereby pinching the configured sheets at apressure of 5 psig pneumaticaly driven together by 2 steel cylinders of1.5″ diameter with 1″ of the layers protruding beyond the exit side ofthe rollers. Approximately 2 mL of the dual-cure mixture was placedbetween the two PET sheets near the nip point on the input side of therollers. The dual-cure was deposited in an even bead manner from asyringe having an opening of about 1 mm. The two roll laminator was thenactuated at a speed of 3 ft/minute, driving the configuration throughthe nips and dispersing the dual-cure mixture between the two PET sheetsand sealing the two PET sheets together with a thin film of dual-cureresin in between. The two roll laminator was stopped prior to the twoPET sheets passing completely through the nip point, such that about 1inch of PET remained above the input side of the rollers.

Step 3: The PET/dual-cure resin/PET laminate was then UV cured in a UVflood lamp (ELC-4001 from Electro-Lite Corp, Bethel, Conn.) (Mercury arclamp with an output range of 290-420 nm (365 nm peak)) and illuminatedfor 1 minute at approximately 3 inches from the lamp. Prior tosubjecting the PET/dual-cure resin/PET laminate to the UV cure, the UVflood lamp was allowed to warm-up for about 10 minutes to reach fulloperating potential.

Step 4: Next, the UV-cured PET/dual-cure resin/PET laminate was placedin a thermal oven set at, and preheated to, 100° C. for 10 minutes.Following this, the PET/dual-cure/PET laminate was allowed to cool atroom temperature for 1 minute before the PET sheets were separated byhand by peeling the two PET sheets apart at a rate of about 1 inch persecond. The sheets separated cleanly with the dual-cure resin remainingon the PET non-Melinex 453 side of the laminate and the Melinex 453treated side peeling off free of dual-cure resin.

Step 5: Separately, the UV curable PFPE resin, having the formula inScheme 2 of Example 1, was mixed by hand for more than about 2 minutesat room temperature in a glass vial with 2.0% by weightdiethoxyacetophenone.

Step 6: Next, a 6″ silicon master containing a patterned array of 2 μm×2μm×0.7 μm cuboidal posts was configured with the PET/dual-cure laminatesheet, formed in Steps 1-4, such that the dual-cure side was facing thepatterned side of the wafer. The laminate and the wafer were insertedinto a two roll laminator having two different size rollers. One rolleris a 16 mm diameter rubber coated roller, 9″ in length with a shorehardness of 30 and the other roller is a 30 mm diameter aluminum roller9″ in length. The rollers were closed, thereby pinching the configuredsheets at a pressure of 5 psig pneumaticaly driven by two steelcylinders of 1.5″ diameter with 1″ of the layers protruding beyond theexit side of the rollers. Approximately 1 mL of the UV-curable PFPEcompound, described in Step 5, was evenly placed between thePET/dual-cure sheet and the wafer near the nip point on the inlet sideof the rollers. The UV-curable PFPE was disposed in a bead pattern froma syringe having an opening of about 1 mm. The laminator was thenactuated at a speed of 3 ft/minute, laminating the PET/dual cure sheetto the 6″ patterned wafer with a thin film of UV-curable PFPEdistributed in between. The two roll laminator was then stopped whenabout 1 inch of the PET/dual-cure laminate/UV-curable PFPE/siliconmaster remained on the inlet side of the rollers. The rollers werecarefully opened to release the PET/dual-cure laminate/UV-curablePFPE/silicon master laminate.

Step 7: The Dual cure sheet/UV-curable PFPE/Silicon wafer laminate wasexposed to UV light through the PET sheet using a UV flood lamp(ELC-4001 from Electro-Lite Corp, Bethel, Conn.) (Mercury arc lamp withan output range of 290-420 nm (365 nm peak)) and were illuminated for 1minute approximately 3 inches from the lamp. Prior to exposing thedual-cure sheet/UV-curable PFPE/silicon wafer laminate to the UVfloodlamp, the UV light source was allowed to warm up for 10 minutes.After exposure for 10 minutes, the light was extinguished and thedual-cure sheet/UV-curable PFPE/silicon wafer laminate was removed.Following removal from the floodlamp, the dual-cure sheet/UV-curablePFPE layer was carefully separated, by hand peeling at about 1 inch persecond from the silicon master. Upon separation, a thin (10-20 micron)PFPE layer was adhered to the dual-cure adhered to the PET and the thinPFPE layer included features of the etched silicon wafers.

Example 3

Step 1: To form an adhesion promoter for PFPE molds to PET, a dual-curecomposition of the PFPE structures, shown in Scheme 1 or Example 1, wasmixed by hand stir for at least 2 minutes at room temperature in a glassvial. In particular, the dual-cure composition of PFPE structuresincludes the structures shown in Scheme 1 of Example 1 with 2.0% byweight diethoxyacetophenone photoinitiator and 0.1% by weight dibutyltindiacetate catalyst.

Step 2: One 6″×12″×7 mil sheet of Melinex 453 (Dupont Teijin Films)polyethylene terephthalate) (PET) and one 6″×12″×4 mil sheet of Melinex454 (amine functionalized) (Dupont Teijin Films) PET were prepared. Thetwo sheets were then configured with the Melinex 453 PET treated sidefacing an untreated side of the Melinex 454 PET sheet. The configuredsheets were inserted into a two roll laminator having two different sizerollers. One roller is a 16 mm diameter rubber coated roller, 9″ inlength with a shore hardness of 30 and the other roller is a 30 mmdiameter aluminum roller 9″ in length. The rollers were closed, therebypinching the configured sheets at a pressure of 5 psig pneumaticalydriven together by two steel cylinders of 1.5″ diameter with 1″ of thelayers protruding beyond the exit side of the rollers. Approximately 2mL of the dual-cure mixture was placed between the two PET sheets nearthe nip point on the input side of the rollers. The dual-cure wasdeposited in an even bead manner from a syringe having an opening ofabout 1 mm. The two roll laminator was then actuated at a speed of 3ft/minute, driving the configuration through the nips and dispersing thedual-cure mixture between the two PET sheets and sealing the two PETsheets together with a thin film of dual-cure resin in between. The tworoll laminator was stopped prior to the two PET sheets passingcompletely through the nip point, such that about 1 inch of PET remainedabove the input side of the rollers.

Step 3: The Melinex 454 PET/dual-cure resin/Melinex 453 PET laminate wasthen UV cured in a UV flood lamp (ELC-4001 from Electro-Lite Corp,Bethel, Conn.) (Mercury arc lamp with an output range of 290-420 nm (365nm peak)) and illuminated for 1 minute at approximately 3 inches fromthe lamp. Prior to subjecting the Melinex 454 PET/dual-cureresin/Melinex 453 PET laminate to the UV cure, the UV flood lamp wasallowed to warm-up for about 10 minutes to reach full operatingpotential.

Step 4: Next, the UV-cured Melinex 454 PET/dual-cure resin/Melinex 453PET laminate was placed in a thermal oven set at, and preheated to, 100°C. for 10 minutes. Following this, the laminate was allowed to cool atroom temperature for 1 minute before the PET sheets were separated byhand by peeling the two PET sheets apart at a rate of about 1 inch persecond. The sheets separated cleanly with the dual-cure resin remainingon the Melinex 454 PET sheet of the laminate and the Melinex 453 treatedside peeling off free of dual-cure resin.

Step 5: Separately, the UV curable PFPE resin, having the formula inScheme 2 of Example 1, was mixed by hand for more than about 2 minutesat room temperature in a glass vial with 2.0% by weightdiethoxyacetophenone.

Step 6: Next, a 6″ silicon master containing a patterned array of 2 μm×2μm×0.7 μm cuboidal posts was configured with the Melinex 454PET/dual-cure laminate sheet, formed in Steps 1-4, such that thedual-cure side was facing the patterned side of the wafer. The laminateand the wafer were inserted into a two roll laminator having twodifferent size rollers. One roller is a 16 mm diameter rubber coatedroller, 9″ in length with a shore hardness of 30 and the other roller isa 30 mm diameter aluminum roller 9″ in length. The rollers were closed,thereby pinching the configured sheets at a pressure of 5 psigpneumaticaly driven together by two steel cylinders of 1.5″ diameterwith 1″ of the layers protruding beyond the exit side of the rollers.Approximately 1 mL of the UV-curable PFPE compound, described in Step 5,was evenly placed between the Melinex 454 PET/dual-cure sheet and thewafer near the nip point on the inlet side of the rollers. TheUV-curable PFPE was disposed in a bead pattern from a syringe having anopening of about 1 mm. The laminator was then actuated at a speed of 3ft/minute, laminating the Melinex 454 PET/dual cure sheet to the 6″patterned wafer with a thin film of UV-curable PFPE distributed inbetween. The two roll laminator was then stopped when about 1 inch ofthe Melinex 454 PET/dual-cure laminate/UV-curable PFPE/silicon masterremained on the inlet side of the rollers. The rollers were carefullyopened to release the Melinex 454 PET/dual-cure laminate/UV-curablePFPE/silicon master laminate.

Step 7: The Dual cure sheet/UV-curable PFPE/Silicon wafer laminate wasexposed to UV light through the Melinex 454 PET sheet using a UV floodlamp (ELC-4001 from Electro-Lite Corp, Bethel, Conn.) (Mercury arc lampwith an output range of 290-420 nm (365 nm peak)) and were illuminatedfor 1 minute approximately 3 inches from the lamp. Prior to exposing thedual-cure sheet/UV-curable PFPE/silicon wafer laminate to the UVfloodlamp, the UV light source was allowed to warm up for 10 minutes.After exposure for 10 minutes, the light was extinguished and thedual-cure sheet/UV-curable PFPE/silicon wafer laminate was removed.Following removal from the floodlamp, the dual-cure sheet/UV-curablePFPE layer was carefully separated, by hand peeling at about 1 inch persecond from the silicon master. Upon separation, a thin (10-20 micron)PFPE layer was adhered to the dual-cure adhered to the PET and the thinPFPE layer included features of the etched silicon wafers.

Example 4

Step 1: To form an adhesion promoter for PFPE molds to PET, a dual-curecomposition of the PFPE structures, shown in Scheme 1 of Example 1, wasmixed by hand stir for at least 2 minutes at room temperature in a glassvial. In particular, the dual-cure composition of PFPE structuresincludes the structures shown in Scheme 1 of Example 1 with 2.0% byweight diethoxyacetophenone photoinitiator and 0.1% by weight dibutyltindiacetate catalyst.

Step 2: One 6″×12″×7 mil sheet of Melinex 453 (Dupont Teijin Films)poly(ethylene terephthalate) (PET) and one 6″×12″×4 mil sheet of Melinex582 (carboxyl functionalized) (Dupont Teijin Films) PET were prepared.The two sheets were then configured with the Melinex 453 PET treatedside facing an untreated side of the Melinex 582 PET sheet. Theconfigured sheets were inserted into a two roll laminator having twodifferent size rollers. One roller is a 16 mm diameter rubber coatedroller, 9″ in length with a shore hardness of 30 and the other roller isa 30 mm diameter aluminum roller 9″ in length. The rollers were closed,thereby pinching the configured sheets at a pressure of 5 psigpneumaticaly driven together by two steel cylinders of 1.5″ diameterwith 1 inch of the layers protruding beyond the exit side of therollers. Approximately 2 mL of the dual-cure mixture was placed betweenthe two PET sheets near the nip point on the input side of the rollers.The dual-cure was deposited in an even bead manner from a syringe havingan opening of about 1 mm. The two roll laminator was then actuated at aspeed of 3 ft/minute, driving the configuration through the nips anddispersing the dual-cure mixture between the two PET sheets and sealingthe two PET sheets together with a thin film of dual-cure resin inbetween. The two roll laminator was stopped prior to the two PET sheetspassing completely through the nip point, such that about 1 inch of PETremained above the input side of the rollers.

Step 3: The Melinex 582 PET/dual-cure resin/Melinex 453 PET laminate wasthen UV cured in a UV flood lamp (ELC-4001 from Electro-Lite Corp,Bethel, Conn.) (Mercury arc lamp with an output range of 290-420 nm (365nm peak)) and illuminated for 1 minute at approximately 3 inches fromthe lamp. Prior to subjecting the Melinex 582 PET/dual-cureresin/Melinex 453 PET laminate to the UV cure, the UV flood lamp wasallowed to warm-up for about 10 minutes to reach full operatingpotential.

Step 4: Next, the UV-cured Melinex 582 PET/dual-cure resin/Melinex 453PET laminate was placed in a thermal oven set at, and preheated to, 100°C. for 10 minutes. Following this, the laminate was allowed to cool atroom temperature for 1 minute before the PET sheets were separated byhand by peeling the two PET sheets apart at a rate of about 1 inch persecond. The sheets separated cleanly with the dual-cure resin remainingon the Melinex 582 PET sheet of the laminate and the Melinex 453 treatedside peeling off free of dual-cure resin.

Step 5: Separately, the UV curable PFPE resin, having the formula inScheme 2 of Example 1, was mixed by hand for more than about 2 minutesat room temperature in a glass vial with 2.0% by weightdiethoxyacetophenone.

Step 6: Next, a 6″ silicon master containing a patterned array of 2 μm×2μm×1.4 μm cuboidal posts was configured with the Melinex 582PET/dual-cure laminate sheet, formed in Steps 1-4, such that thedual-cure side was facing the patterned side of the wafer. The laminateand the wafer were inserted into a two roll laminator having twodifferent size rollers. One roller is a 16 mm diameter rubber coatedroller, 9″ in length with a shore hardness of 30 and the other roller isa 30 mm diameter aluminum roller 9″ in length. The rollers were closed,thereby pinching the configured sheets at a pressure of 5 psigpneumaticaly driven together by two steel cylinders of 1.5″ diameterwith 1 inch of the layers protruding beyond the exit side of therollers. Approximately 1 mL of the UV-curable PFPE compound, describedin Step 5, was evenly placed between the Melinex 582 PET/dual-cure sheetand the wafer near the nip point on the inlet side of the rollers. TheUV-curable PFPE was disposed in a bead pattern from a syringe having anopening of about 1 mm. The laminator was then actuated at a speed of 3ft/minute, laminating the Melinex 582 PET/dual cure sheet to the 6″patterned wafer with a thin film of UV-curable PFPE distributed inbetween. The two roll laminator was then stopped when about 1 inch ofthe Melinex 582 PET/dual-cure laminate/UV-curable PFPE/silicon masterremained on the inlet side of the rollers. The rollers were carefullyopened to release the Melinex 582 PET/dual-cure laminate/UV-curablePFPE/silicon master laminate.

Step 7: The Dual cure sheet/UV-curable PFPE/Silicon wafer laminate wasexposed to UV light through the Melinex 582 PET sheet using a UV floodlamp (ELC-4001 from Electro-Lite Corp, Bethel, Conn.) (Mercury arc lampwith an output range of 290-420 nm (365 nm peak)) and were illuminatedfor 1 minute approximately 3 inches from the lamp. Prior to exposing thedual-cure sheet/UV-curable PFPE/silicon wafer laminate to the UVfloodlamp, the UV light source was allowed to warm up for 10 minutes.After exposure for 10 minutes, the light was extinguished and thedual-cure sheet/UV-curable PFPE/silicon wafer laminate was removed.Following removal from the floodlamp, the dual-cure sheet/UV-curablePFPE layer was carefully separated, by hand peeling at about 1 inch persecond from the silicon master. Upon separation, a thin (10-20 micron)PFPE layer was adhered to the dual-cure adhered to the PET and the thinPFPE layer included features of the etched silicon wafers.

Example 5

Step 1: To form an adhesion promoter for PFPE molds to PET, a dual-curecomposition of the PFPE structures, shown in Scheme 1 of Example 1, wasmixed by hand stir for at least 2 minutes at room temperature in a glassvial. In particular, the dual-cure composition of PFPE structuresincludes the structures shown in Scheme 1 of Example 1 with 2.0% byweight diethoxyacetophenone photoinitiator and 0.1% by weight dibutyltindiacetate catalyst.

Step 2: Two 6″×12″×7 mil sheets of Melinex 453 (Dupont Teijin Films)poly(ethylene terephthalate) (PET) were cut. The two sheets were thenconfigured with a treated side of one sheet facing an untreated side ofthe other sheet, however, untreated side was treated with a 1 minutecorona treatment. The configured sheets were inserted into a two rolllaminator having two different size rollers. One roller is a 16 mmdiameter rubber coated roller, 9″ in length with a shore hardness of 30and the other roller is a 30 mm diameter aluminum roller 9″ in length.The rollers were closed, thereby pinching the configured sheets at apressure of 5 psig pneumaticaly driven together by two steel cylindersof 1.5″ diameter with 1 inch of the layers protruding beyond the exitside of the rollers. Approximately 2 mL of the dual-cure mixture wasplaced between the two PET sheets near the nip point on the input sideof the rollers. The dual-cure was deposited in an even bead manner froma syringe having an opening of about 1 mm. The two roll laminator wasthen actuated at a speed of 3 ft/minute, driving the configurationthrough the nips and dispersing the dual-cure mixture between the twoPET sheets and sealing the two PET sheets together with a thin film ofdual-cure resin in between. The two roll laminator was stopped prior tothe two PET sheets passing completely through the nip point, such thatabout 1 inch of PET remained above the input side of the rollers.

Step 3: The PET/dual-cure resin/PET laminate was then UV cured in a UVflood lamp (ELC-4001 from Electro-Lite Corp, Bethel, Conn.) (Mercury arclamp with an output range of 290-420 nm (365 nm peak)) and illuminatedfor 1 minute at approximately 3 inches from the lamp. Prior tosubjecting the PET/dual-cure resin/PET laminate to the UV cure, the UVflood lamp was allowed to warm-up for about 10 minutes to reach fulloperating potential.

Step 4: Next, the UV-cured PET/dual-cure resin/PET laminate was placedin a thermal oven set at, and preheated to, 100° C. for 10 minutes.Following this, the PET/dual-cure/PET laminate was allowed to cool atroom temperature for 1 minute before the PET sheets were separated byhand by peeling the two PET sheets apart at a rate of about 1 inch persecond. The sheets separated cleanly with the dual-cure resin remainingon the 1 minute corona treated PET non-Melinex 453 side of the laminateand the Melinex 453 treated side peeling off free of dual-cure resin.

Step 5: Separately, the UV curable PFPE resin, having the formula inScheme 2 of Example 1, was mixed by hand for more than about 2 minutesat room temperature in a glass vial with 2.0% by weightdiethoxyacetophenone.

Step 6: Next, a 6″ silicon master containing a patterned array of 2 μm×2μm×0.7 μm cuboidal posts was configured with the PET/dual-cure laminatesheet, formed in Steps 1-4, such that the dual-cure side was facing thepatterned side of the wafer. The laminate and the wafer were insertedinto a two roll laminator having two different size rollers. One rolleris a 16 mm diameter rubber coated roller, 9″ in length with a shorehardness of 30 and the other roller is a 30 mm diameter aluminum roller9″ in length. The rollers were closed, thereby pinching the configuredsheets at a pressure of 5 psig pneumaticaly driven together by two steelcylinders of 1.5″ diameter with 1 inch of the layers protruding beyondthe exit side of the rollers. Approximately 1 mL of the UV-curable PFPEcompound, described in Step 5, was evenly placed between thePET/dual-cure sheet and the wafer near the nip point on the inlet sideof the rollers. The UV-curable PFPE was disposed in a bead pattern froma syringe having an opening of about 1 mm. The laminator was thenactuated at a speed of 3 ft/minute, laminating the PET/dual cure sheetto the 6″ patterned wafer with a thin film of UV-curable PFPEdistributed in between. The two roll laminator was then stopped whenabout 1 inch of the PET/dual-cure laminate/UV-curable PFPE/siliconmaster remained on the inlet side of the rollers. The rollers werecarefully opened to release the PET/dual-cure laminate/UV-curablePFPE/silicon master laminate.

Step 7: The Dual cure sheet/UV-curable PFPE/Silicon wafer laminate wasexposed to UV light through the PET sheet using a UV flood lamp(ELC-4001 from Electro-Lite Corp, Bethel, Conn.) (Mercury arc lamp withan output range of 290-420 nm (365 nm peak)) and were illuminated for 1minute approximately 3 inches from the lamp. Prior to exposing thedual-cure sheet/UV-curable PFPE/silicon wafer laminate to the UVfloodlamp, the UV light source was allowed to warm up for 10 minutes.After exposure for 10 minutes, the light was extinguished and thedual-cure sheet/UV-curable PFPE/silicon wafer laminate was removed.Following removal from the floodlamp, the dual-cure sheet/UV-curablePFPE layer was carefully separated, by hand peeling at about 1 inch persecond from the silicon master. Upon separation, a thin (10-20 micron)PFPE layer was adhered to the dual-cure adhered to the PET and the thinPFPE layer included features of the etched silicon wafers.

Example 6

Step 1: To form an adhesion promoter for PFPE molds to polycarbonate, adual-cure composition of the PFPE structures, shown in Scheme 1 ofExample 1, was mixed by hand stir for at least 2 minutes at roomtemperature in a glass vial. In particular, the dual-cure composition ofPFPE structures includes the structures shown in Scheme 1 of Example 1with 2.0% by weight diethoxyacetophenone photoinitiator and 0.1% byweight dibutyltin diacetate catalyst.

Step 2: One 6″×12″×7 mil sheet of Melinex 453 (Dupont Teijin Films)poly(ethylene terephthalate) (PET) and one 6″×12″×6.5 mil sheet ofpolycarbonate (PC) were cut. The two sheets were then configured with atreated side of the PET sheet facing the sheet of PC. The configuredsheets were inserted into a two roll laminator having two different sizerollers. One roller is a 16 mm diameter rubber Coated roller, 9″ inlength with a shore hardness of 30 and the other roller is a 30 mmdiameter aluminum roller 9″ in length. The rollers were closed, therebypinching the configured sheets at a pressure of 5 psig pneumaticalydriven together by two steel cylinders of 1.5″ diameter with 1 inch ofthe layers protruding beyond the exit side of the rollers. Approximately2 mL of the dual-cure mixture was placed between the PET/PC sheets nearthe nip point on the input side of the rollers. The dual-cure wasdeposited in an even bead manner from a syringe having an opening ofabout 1 mm. The two roll laminator was then actuated at a speed of 3ft/minute, driving the configuration through the nips and dispersing thedual-cure mixture between the PET/PC sheets and sealing the PET/PCsheets together with a thin film of dual-cure resin in between. The tworoll laminator was stopped prior to the PET/PC sheets passing completelythrough the nip point, such that about 1 inch of the PET/PC sheetsremained above the input side of the rollers.

Step 3: The PC/dual-cure resin/PET laminate was then UV cured in a UVflood lamp (ELC-4001 from Electro-Lite Corp, Bethel, Conn.) (Mercury arclamp with an output range of 290-420 nm (365 nm peak)) and illuminatedfor 1 minute at approximately 3 inches from the lamp. Prior tosubjecting the PC/dual-cure resin/PET laminate to the UV cure, the UVflood lamp was allowed to warm-up for about 10 minutes to reach fulloperating potential.

Step 4: Next, the UV-cured PC/dual-cure resin/PET laminate was placed ina thermal oven set at, and preheated to, 100° C. for 10 minutes.Following this, the PC/dual-cure/PET laminate was allowed to cool atroom temperature for 1 minute before the PET/PC sheets were separated byhand by peeling the PET/PC sheets apart at a rate of about 1 inch persecond. The sheets separated cleanly with the dual-cure resin remainingon the PC side of the laminate and the Melinex 453 treated PET peelingoff free of dual-cure resin.

Step 5: Separately, the UV curable PFPE resin, having the formula inScheme 2 of Example 1, was mixed by hand for more than about 2 minutesat room temperature in a glass vial with 2.0% by weightdiethoxyacetophenone.

Step 6: Next, a 6″ silicon master containing a patterned array of 2 μm×2μm×0.7 μm cuboidal posts was configured with the PC/dual-cure laminatesheet, formed in Steps 1-4, such that the dual-cure side was facing thepatterned side of the wafer. The laminate and the wafer were insertedinto a two roll laminator having two different size rollers. One rolleris a 16 mm diameter rubber coated roller, 9″ in length with a shorehardness of 30 and the other roller is a 30 mm diameter aluminum roller9″ in length. The rollers were closed, thereby pinching the configuredsheets at a pressure of 5 psig pneumaticaly driven together by two steelcylinders of 1.5″ diameter with 1 inch of the layers protruding beyondthe exit side of the rollers. Approximately 1 mL of the UV-curable PFPEcompound, described in Step 5, was evenly placed between thePC/dual-cure sheet and the wafer near the nip point on the inlet side ofthe rollers. The UV-curable PFPE was disposed in a bead pattern from asyringe having an opening of about 1 mm. The laminator was then actuatedat a speed of 3 ft/minute, laminating the PC/dual cure sheet to the 6″patterned wafer with a thin film of UV-curable PFPE distributed inbetween. The two roll laminator was then stopped when about 1 inch ofthe PC/dual-cure laminate/UV-curable PFPE/silicon master remained on theinlet side of the rollers. The rollers were carefully opened to releasethe PC/dual-cure laminate/UV-curable PFPE/silicon master laminate.

Step 7: The Dual cure sheet/UV-curable PFPE/Silicon wafer laminate wasexposed to UV light through the PC sheet using a UV flood lamp (ELC-4001from Electro-Lite Corp, Bethel, Conn.) (Mercury arc lamp with an outputrange of 290-420 nm (365 nm peak)) and were illuminated for 1 minuteapproximately 3 inches from the lamp. Prior to exposing the dual-curesheet/UV-curable PFPE/silicon wafer laminate to the UV floodlamp, the UVlight source was allowed to warm up for 10 minutes. After exposure for10 minutes, the light was extinguished and the dual-curesheet/UV-curable PFPE/silicon wafer laminate was removed. Followingremoval from the floodlamp, the dual-cure sheet/UV-curable PFPE layerwas carefully separated, by hand peeling at about 1 inch per second fromthe silicon master. Upon separation, a thin (10-20 micron) PFPE layerwas adhered to the dual-cure adhered to the PET and the thin PFPE layerincluded features of the etched silicon wafers.

Example 7

Step 1: To form an adhesion promoter for PFPE molds to silicon rubber, adual-cure composition of the PFPE structures, shown in Scheme 1 ofExample 1, was mixed by hand stir for at least 2 minutes at roomtemperature in a glass vial. In particular, the dual-cure composition ofPFPE structures includes the structures shown in Scheme 1 of Example 1with 2.0% by weight diethoxyacetophenone photoinitiator and 0.1% byweight dibutyltin diacetate catalyst.

Step 2: One 6″×12″×7 mil sheet of Melinex 453 (Dupont Teijin Films)polyethylene terephthalate) (PET) and one 6″×12″×10 mil sheet of coronatreated silicone rubber (SR) were cut. The two sheets were thenconfigured with the corona treated side of the silicone rubber sheetfacing a treated side of the PET sheet. The configured sheets wereinserted into a two roll laminator having two different size rollers.One roller is a 16 mm diameter rubber coated roller, 9″ in length with ashore hardness of 30 and the other roller is a 30 mm diameter aluminumroller 9″ in length. The rollers were closed, thereby pinching theconfigured sheets at a pressure of 5 psig pneumaticaly driven togetherby two steel cylinders of 1.5″ diameter with 1 inch of the layersprotruding beyond the exit side of the rollers. Approximately 2 mL ofthe dual-cure mixture was placed between the SR/PET sheets near the nippoint on the input side of the rollers. The dual-cure was deposited inan even bead manner from a syringe having an opening of about 1 mm. Thetwo roll laminator was then actuated at a speed of 3 ft/minute, drivingthe configuration through the nips and dispersing the dual-cure mixturebetween the SR/PET sheets and sealing the SR/PET sheets together with athin film of dual-cure resin in between. The two roll laminator wasstopped prior to the SR/PET sheets passing completely through the nippoint, such that about 1 inch of SR/PET remained above the input side ofthe rollers. Step 3: The SR/dual-cure resin/PET laminate was then UVcured in a UV flood lamp (ELC-4001 from Electro-Lite Corp, Bethel,Conn.) (Mercury arc lamp with an output range of 290-420 nm (365 nmpeak)) and illuminated for 1 minute at approximately 3 inches from thelamp. Prior to subjecting the SR/dual-cure resin/PET laminate to the UVcure, the UV flood lamp was allowed to warm-up for about 10 minutes toreach full operating potential.

Step 4: Next, the UV-cured SR/dual-cure resin/PET laminate was placed ina thermal oven set at, and preheated to, 100° C. for 10 minutes.Following this, the SR/dual-cure/PET laminate was allowed to cool atroom temperature for 1 minute before the SR/PET sheets were separated byhand by peeling the SR/PET sheets apart at a rate of about 1 inch persecond. The sheets separated cleanly with the dual-cure resin remainingon the SR sheet and the Melinex 453 treated PET side peeling off free ofdual-cure resin.

Step 5: Separately, the UV curable PFPE resin, having the formula inScheme 2 of Example 1, was mixed by hand for more than about 2 minutesat room temperature in a glass vial with 2.0% by weightdiethoxyacetophenone.

Step 6: Next, a 6″ silicon master containing a patterned array of 2 μm×2μm×1.4 μm cuboidal posts was configured with the SR/dual-cure laminatesheet, formed in Steps 1-4, such that the dual-cure side was facing thepatterned side of the wafer. The laminate and the wafer were insertedinto a two roll laminator having two different size rollers. One rolleris a 16 mm diameter rubber coated roller, 9″ in length with a shorehardness of 30 and the other roller is a 30 mm diameter aluminum roller9″ in length. The rollers were closed, thereby pinching the configuredsheets at a pressure of 5 psig pneumaticaly driven together by two steelcylinders of 1.5″ diameter with 1 inch of the layers protruding beyondthe exit side of the rollers. Approximately 1 mL of the UV-curable PFPEcompound, described in Step 5, was evenly placed between theSR/dual-cure sheet and the wafer near the nip point on the inlet side ofthe rollers. The UV-curable PFPE was disposed in a bead pattern from asyringe having an opening of about 1 mm. The laminator was then actuatedat a speed of 3 ft/minute, laminating the SR/dual cure sheet to the 6″patterned wafer with a thin film of UV-curable PFPE distributed inbetween. The two roll laminator was then stopped when about 1 inch ofthe SR/dual-cure laminate/UV-curable PFPE/silicon master remained on theinlet side of the rollers. The rollers were carefully opened to releasethe SR/dual-cure laminate/UV-curable PFPE/silicon master laminate.

Step 7: The Dual cure sheet/UV-curable PFPE/Silicon wafer laminate wasexposed to UV light through the SR sheet using a UV flood lamp (ELC-4001from Electro-Lite Corp, Bethel, Conn.) (Mercury arc lamp with an outputrange of 290-420 nm (365 nm peak)) and were illuminated for 1 minuteapproximately 3 inches from the lamp. Prior to exposing the dual-curesheet/UV-curable PFPE/silicon wafer laminate to the UV floodlamp, the UVlight source was allowed to warm up for 10 minutes. After exposure for10 minutes, the light was extinguished and the dual-curesheet/UV-curable PFPE/silicon wafer laminate was removed. Followingremoval from the floodlamp, the dual-cure sheet/UV-curable PFPE layerwas carefully separated, by hand peeling at about 1 inch per second fromthe silicon master. Upon separation, a thin (10-20 micron) PFPE layerwas adhered to the dual-cure adhered to the SR and the thin PFPE layerincluded features of the etched silicon wafers.

Example 8

Step 1: To form an adhesion promoter for PFPE molds to PET, a dual-curecomposition of the PFPE structures, shown in Scheme 1 of Example 1, wasmixed by hand stir for at least 2 minutes at room temperature in a glassvial. In particular, the dual-cure composition of PFPE structuresincludes the structures shown in Scheme 1 of Example 1 with 2.0% byweight diethoxyacetophenone photoinitiator and 0.1% by weight dibutyltindiacetate catalyst.

Step 2: One 6″×12″×7 mil sheet of untreated poly(ethylene terephthalate)(PET) was cut. The PET sheet was configured adjacent a 6″ silicon mastercontaining a patterned array of 2 μm×2 μm×1.4 μm cuboidal posts. Theconfigured PET sheet/silicon wafer master were inserted into a two rolllaminator having two different size rollers. One roller is a 16 mmdiameter rubber coated roller, 9″ in length with a shore hardness of 30and the other roller is a 30 mm diameter aluminum roller 9″ in length.The rubber roller was positioned adjacent the silicon master and thealuminum roller was positioned adjacent the PC. The rollers were closed,thereby pinching the configured sheets at a pressure of 5 psigpneumaticaly driven together by two steel cylinders of 1.5″ diameterwith 1 inch of the layers protruding beyond the exit side of therollers. Approximately 2 mL of the dual-cure mixture was placed betweenthe PET/master configuration near the nip point on the input side of therollers. The dual-cure was deposited in an even bead manner from asyringe having an opening of about 1 mm. The two roll laminator was thenactuated at a speed of 3 ft/minute, driving the configuration throughthe nips and dispersing the dual-cure mixture between the PET/masterconfiguration and sealing the PET/master configuration together with athin film of dual-cure resin in between. The two roll laminator wasstopped prior to the PET/master configuration passing completely throughthe nip point, such that about 1 inch of PET/master configurationremained above the input side of the rollers.

Step 3: The PET/dual-cure resin/master laminate was then UV cured in aUV flood lamp (ELC-4001 from Electro-Lite Corp, Bethel, Conn.) (Mercuryarc lamp with an output range of 290-420 nm (365 nm peak)) andilluminated for 3 minutes at approximately 3 inches from the lamp. Priorto subjecting the PET/dual-cure resin/master laminate to the UV cure,the UV flood lamp was allowed to warm-up for about 10 minutes to reachfull operating potential.

Step 4: Next, the UV-cured PET/dual-cure resin/master laminate wasplaced in a thermal oven set at, and preheated to, 115° C. for 3 hours.Following this, the PET/dual-cure/master laminate was allowed to cool atroom temperature for 1 minute before the PET sheet was separated fromthe master by hand by peeling the PET sheet away at a rate of about 1inch per second. Following this, the PET/dual-cure laminate wasseparated cleanly from the master wafer to reveal a patterned dual-curemold adhered to the PET.

Example 9

Step 1: To form an adhesion promoter for PFPE molds to PET, a UV curablecomposition of the PFPE structures, shown in Scheme 2 of Example 1, wasmixed by hand stir for at least 2 minutes at room temperature in a glassvial. In particular, the UV-curable composition of PFPE structuresincludes the structure shown in Scheme 2 of Example 1 and 2.0% by weightdiethoxyacetophenone.

Step 2: One 6″×12″×6.5 mil sheet of polycarbonate (PC) was cut. The PCsheet was configured adjacent a 6″ silicon master containing a patternedarray of 2 μm×2 μm×1.4 μm cuboidal posts. The configured PC/siliconmaster was inserted into a two roll laminator having two different sizerollers. One roller is a 16 mm diameter rubber coated roller, 9″ inlength with a shore hardness of 30 and the other roller is a 30 mmdiameter aluminum roller 9″ in length. The rubber coated roller waspositioned adjacent the silicon master and the aluminum roller waspositioned adjacent the PC. The rollers were closed, thereby pinchingthe configured sheets at a pressure of 5 psig pneumaticaly driventogether by two steel cylinders of 1.5″ diameter with 1 inch of thelayers protruding beyond the exit side of the rollers. Approximately 2mL of the UV-curable mixture was placed between the PC/masterconfiguration near the nip point on the input side of the rollers. TheUV-curable mixture was deposited in an even bead manner from a syringehaving an opening of about 1 mm. The two roll laminator was thenactuated at a speed of 3 ft/minute, driving the configuration throughthe nips and dispersing the UV-curable mixture between the PC/masterconfiguration and sealing the PC/master configuration together with athin film of UV-curable mixture in between. The two roll laminator wasstopped prior to the PC/master configuration passing completely throughthe nip point, such that about 1 inch of PC/master configurationremained above the input side of the rollers.

Step 3: The PC/UV-curable mixture/master laminate was then UV cured in aUV flood lamp (ELC-4001 from Electro-Lite Corp, Bethel, Conn.) (Mercuryarc lamp with an output range of 290-420 nm (365 nm peak)) andilluminated for 3 minutes at approximately 3 inches from the lamp. Priorto subjecting the PC/UV-curable mixture/master laminate to the UV cure,the UV flood lamp was allowed to warm-up for about 10 minutes to reachfull operating potential.

Step 4: Next, the PC/UV-curable mixture laminate was separated cleanlyfrom the master wafer to reveal a patterned UV-curable mold adhered tothe PC.

Example 10 Gel Fraction

Dual cure materials are synthesized as given previously. For eachsample, approximately 2 g of uncured material is weighed into a 20 mLglass vial of known weight. Between samples, the material is stored in adesiccator. For thermal tests, the vials are labeled as T1-T7, for uvcuring, the vials are labeled as U1-U6. IR spectra were taken of allsamples. FIGS. 7A and 7B are graphs showing sample IR data.

For the thermal cure tests, a digital convection oven is set to 100° C.The vial is placed in the oven for the determined amount of time (10sec, 30 sec, 1 min, 2 min, 4 min, 8 min, or 12 min). The vial is removedfrom the oven and allowed to cool to room temperature. The sample ischecked for fiber formation using tweezers, in a manner similar to a“toothpick test”, known to those skilled in the art. The sample vial isthen filled with approximately 20 mL of SOLKANE™(1,1,1,3,3-pentafluorobutane) (Solvay Solexis, Brussels, Belgium) andshaken for 2 minutes to extract the sol fraction. The liquid is decantedoff and passed through a 45 μm filter into a glass vial of known weight,labeled as T1a, T2a, etc. All vials are placed in a vacuum oven andtaken to dryness (about 2 hours). The vials are weighed to determine themasses of the sol fraction and gelled material.

For the uv cure tests, a low power uv oven (24-28 mW/cm² at 365 nm)provided by Electro-lite (Electro-Lite Corporation, Bethel, Conn.). Thevial is placed in the uv oven, purged with nitrogen for 2 minutes, thencured for the determined amount of time (10 sec, 30 sec, 1 min, 2 min, 4min, 8 min, or 12 min). The vial is removed from the uv oven. The sampleis checked for fiber formation using tweezers, in a manner similar to a“toothpick test”, known to those skilled in the art. The sample vial isthen filled with approximately 20 mL of SOLKANE™(1,1,1,3,3-pentafluorobutane) (Solvay Solexis, Brussels, Belgium) andshaken for 2 minutes to extract the sol fraction. The liquid is decantedoff and passed through a 45 μm filter into a glass vial of known weight,labeled as U1a, U2a, etc. All vials are placed in a vacuum oven andtaken to dryness (about 2 hours). The vials are weighed to determine themasses of the sol fraction and gelled material.

Results of Solgel Fraction Study:

Cure Cure % sol Vial # type time fraction T1 Thermal 10 sec 91.56 T2Thermal 30 sec 52.57 T3 Thermal 60 sec 32.58 T4 Thermal 2 min 11.6 T5Thermal 4 min 20.23 T6 Thermal 8 min 7.71 T7 Thermal 12 min 8.81 U1 UV10 sec 76.49 U2 UV 30 sec 81.5 U3 UV 60 sec 23.33 U4 UV 2 min 16.21 U5UV 4 min 3.16 U6 UV 8 min 0.85 Tweezer Test Sample Result T1 N T2 N T3Y/N T4 Y T5 Y Y/N means no fibers initially, but when SOLKANE ™ isadded, a few fibers can be seen in solution T6 Y T7 Y U1 N U2 Y/N U3 YU4 Y U5 Y U6 Y

Samples having properties appropriate for the present applicationsinclude #s T6 and T7 (thermally cured at 100° C. for greater than 8min.) and U5 and U6 (UV cured at 24-28 mW/cm² at 365 nm for greater than4 min).

The invention claimed is:
 1. A laminate nanomold system comprising: alayer of perfluoropolyether, wherein the layer of perfluoropolyetherincludes a first surface defining a plurality of cavities, wherein eachcavity of the plurality of cavities has a predetermined shape and isless than about 10 micrometers in a largest dimension, and wherein thelayer of perfluoropolyether is less than about 75 micrometers inthickness; a support layer bonded to a second surface of the layer ofperfluoropolyether opposite the first surface, wherein the support layerbonded to the layer of perfluoropolyether has a combined modulus greaterthan about 1400 MPa; a sheet positioned to face the first surface of thelayer of perfluoropolyether; a material disposed between the sheet andthe first surface of the layer of perfluoropolyether, the materialconfigured to conform to the cavities of the first surface; and a firstroller and a second roller defining a nip point configured anddimensioned to receive the layer of perfluoropolyether bonded to thesupport layer, the sheet, and the material.
 2. The laminate nanomoldsystem of claim 1, further comprising a tie-layer disposed between thelayer of perfluoropolyether and the support layer to attach the supportlayer with the layer of perfluoropolyether.
 3. The laminate nanomoldsystem of claim 2, wherein the tie-layer comprises a dual cure material.4. The laminate nanomold system of claim 1, wherein each cavity of theplurality of cavities comprise a predetermined shape selected from thegroup consisting of cylindrical, 200 nm diameter cylinders, cuboidal,200 nm cuboidal, crescent, and concave disc.
 5. The laminate nanomoldsystem of claim 1, wherein the plurality of cavities comprise cavitiesof a variety of predetermined shapes.
 6. The laminate nanomold system ofclaim 1, wherein each cavity of the plurality of cavities is less thanabout 5 micrometers in a largest dimension.
 7. The laminate nanomoldsystem of claim 1, wherein each cavity of the plurality of cavities isless than about 1 micrometers in a largest dimension.
 8. The laminatenanomold system of claim 1, wherein each cavity of the plurality ofcavities is less than about 750 nanometers in a largest dimension. 9.The laminate nanomold system of claim 1, wherein each cavity of theplurality of cavities is less than about 500 nanometers in a largestdimension.
 10. The laminate nanomold system of claim 1, wherein eachcavity of the plurality of cavities is less than about 300 nanometers ina largest dimension.
 11. The laminate nanomold system of claim 1,wherein each cavity of the plurality of cavities is less than about 200nanometers in a largest dimension.
 12. The laminate nanomold system ofclaim 1, wherein each cavity of the plurality of cavities is less thanabout 100 nanometers in a largest dimension.
 13. The laminate nanomoldsystem of claim 1, wherein each cavity of the plurality of cavities isless than about 75 nanometers in a largest dimension.
 14. The laminatenanomold system of claim 1, wherein each cavity of the plurality ofcavities is less than about 50 nanometers in a largest dimension. 15.The laminate nanomold system of claim 1, wherein each cavity of theplurality of cavities is less than about 40 nanometers in a largestdimension.
 16. The laminate nanomold system of claim 1, wherein eachcavity of the plurality of cavities is less than about 30 nanometers ina largest dimension.
 17. The laminate nanomold system of claim 1,wherein each cavity of the plurality of cavities is less than about 20nanometers in a largest dimension.
 18. The laminate nanomold system ofclaim 1, wherein each cavity of the plurality of cavities is less thanabout 10 nanometers in a largest dimension.
 19. The laminate nanomoldsystem of claim 1, wherein the perfluoropolyether layer is less thanabout 40 micrometers thick.
 20. The laminate nanomold system of claim 1,wherein the perfluoropolyether layer is less than about 30 micrometersthick.
 21. The laminate nanomold system of claim 1, wherein theperfluoropolyether layer is less than about 20 micrometers thick. 22.The laminate nanomold system of claim 1, wherein the perfluoropolyetherlayer is less than about 15 micrometers thick.
 23. The laminate nanomoldsystem of claim 1, wherein the perfluoropolyether layer is less thanabout 10 micrometers thick.
 24. The laminate nanomold system of claim 1,wherein the support layer comprises a polymer.
 25. The laminate nanomoldsystem of claim 24, wherein the polymer of the support layer comprisespolyethylene terephthalate.
 26. The laminate nanomold system of claim 1,wherein the support layer is less than about 20 mil thick.
 27. Thelaminate nanomold system of claim 1, wherein the support layer is lessthan about 15 mil thick.
 28. The laminate nanomold system of claim 1,wherein the support layer is less than about 10 mil thick.
 29. Thelaminate nanomold system of claim 1, wherein the support layer is lessthan about 5 mil thick.
 30. The laminate nanomold system of claim 1,wherein the support layer introduces a modulus of greater than 1000 tothe laminate.
 31. The laminate nanomold system of claim 3, wherein thelayer of perfluoropolyether is attached to the support layer byphotoinitiator coupling and thermalinitiator coupling.
 32. The laminatenanomold system of claim 1, wherein the perfluoropolyether comprises aphotocurable component.
 33. The laminate nanomold system of claim 1,wherein the layer of perfluoropolyether has a footprint greater thanabout 25 square centimeters.
 34. The laminate nanomold system of claim1, wherein the layer of perfluoropolyether has a footprint greater thanabout 50 square centimeters.
 35. The laminate nanomold system of claim1, wherein the layer of perfluoropolyether has a footprint greater thanabout 100 square centimeters.
 36. The laminate nanomold system of claim1, wherein each cavity of the plurality of cavities is less than about 5micrometers from an adjacent cavity.
 37. The laminate nanomold system ofclaim 1, wherein each cavity of the plurality of cavities is less thanabout 2 micrometer from an adjacent cavity.
 38. The laminate nanomoldsystem of claim 1, wherein each cavity of the plurality of cavities isless than about 1 micrometers from an adjacent cavity.
 39. The laminatenanomold system of claim 1, wherein each cavity of the plurality ofcavities is less than about 750 nanometers from an adjacent cavity. 40.The laminate nanomold system of claim 1, wherein each cavity of theplurality of cavities is less than about 500 nanometers from an adjacentcavity.
 41. The laminate nanomold system of claim 1, wherein theperfluoropolyether has less than about 10 percent sol fraction.
 42. Thelaminate nanomold system of claim 1, wherein the first roller and secondroller are configured and dimensioned to pinch the layer ofperfluoropolyether, the support layer, the sheet, and the material. 43.A laminate nanomold comprising: a layer of perfluoropolyether, whereinthe layer of perfluoropolyether includes a first surface defining aplurality of cavities, wherein each cavity of the plurality of cavitieshas a predetermined shape and is less than about 10 micrometers in alargest dimension, and wherein the layer of perfluoropolyether is lessthan about 75 micrometers in thickness; and a support layer bonded to asecond surface of the layer of perfluoropolyether opposite the firstsurface, wherein the support layer bonded to the layer ofperfluoropolyether has a combined modulus greater than about 1400 MPa.